Fatty acid reaction products of dextrins or dextran formulated with a surfactant

ABSTRACT

Compositions comprising a neutral surfactant or a reaction product thereof and a reaction product of a saccharide polymer and a fatty acid may be obtained in the presence of water and a hydroxide base (optionally in the presence of the neutral surfactant), the saccharide polymer comprising a dextran, a dextrin compound, or any combination thereof. The reaction product of the saccharide polymer and the fatty acid may be present at a concentration effective to lower surface tension of the neutral surfactant. Depending on the fatty acid identity, among other factors, the compositions may promote emulsification or de-emulsification. In addition, the compositions may promote foam formation under appropriate conditions. Treatment fluids comprising the compositions, including foamed treatment fluids, may be introduced into a subterranean formation to perform a treatment operation in which fluid emulsification or de-emulsification may occur. The reaction products may be incorporated in soaps and other personal care products.

BACKGROUND

Amphiphilic compounds having both hydrophobic and hydrophilic regionswithin their molecular structure are commonly referred to as“surfactants” or “surfactant compounds.” By virtue of their molecularstructure, surfactants tend to lower the surface tension at an interfacebetween two components. Surfactants may be found in a wide range ofconsumer and industrial products including, for example, soaps,detergents, cosmetics, pharmaceuticals, and dispersants. In addition,surfactants are also commonly used in the oil and gas industry. Amongother functions in these applications and others, surfactants maypromote solubility of an otherwise sparingly soluble solid, increasefoaming, facilitate emulsification or de-emulsification, and/or lowerviscosity in particular instances. Poor biodegradation, including slowbiodegradation in liquid environments, and/or poor biocompatibility ofsome common synthetic surfactants may impact consumer and industrialproducts and processes incorporating such surfactants.

The recovery of hydrocarbon resources, such as oil and gas, fromsubterranean formations is often performed in conjunction withintroducing one or more subterranean treatment chemicals downhole. Asused herein, the terms “treat,” “treatment,” “treating,” and grammaticalequivalents thereof refer to any compound, fluid, or combination thereofthat is introduced to a subterranean formation with the goal ofachieving a desired function and/or for a desired purpose. A suitabletreatment chemical may be selected based upon particular conditionspresent or anticipated to be present downhole. Environmental andregulatory concerns may also dictate suitable treatment chemicals thatmay be utilized in particular locales. Surfactants are a frequentlyemployed class of treatment chemicals in the oilfield and may performvarious functions downhole.

Oil and other hydrocarbon resources frequently may be present inemulsified form in a subterranean formation. In order to releaseemulsified oil and other hydrocarbon resources to facilitate productionand/or processing thereof after production, a de-emulsifier may be used.Preventing an emulsion from forming downhole may also be desirable inmany instances.

In other instances, introduction of an emulsified fluid into asubterranean formation may be desirable. Alternately, fluids thatundergo emulsification downhole, promote emulsification downhole, invertan existing emulsion downhole, or change the wetting of a surfacedownhole may be used to promote an intended treatment outcome. Innon-limiting examples, an emulsified fluid may have sufficient viscosityto carry particulates to or from the wellbore, such as proppantparticulates, drill cuttings, or bridging agents as non-limitingexamples. Emulsified fluids may likewise facilitate release of ahydrocarbon resource bound to the matrix of a subterranean formation bychanging the surface wetting characteristics. Microemulsion fluids maybe advantageous in many instances, such as by virtue of their opticalclarity and more facile handling. Microemulsion fluids may likewisechange surface wetting characteristics downhole or draw a hydrocarbonresource into the fluid during production.

In the foregoing applications, various types of surfactants may be usedin the oil and gas industry to stabilize an emulsion or to promotede-emulsification of a fluid. In many instances, surfactants capable ofpromoting emulsification or de-emulsification have completely differentchemical structures from one another, and a general class of surfactantcompounds is not readily tunable to the particular conditions that maybe present downhole. Some common surfactants may be expensive, have pooraqueous solubility, and/or be subject to environmental and/or othergovernment regulations. In addition, some emulsifying or de-emulsifyingagents have high surface tension and intrafacial tension values at thecritical micelle concentration and may not be easily pumped downhole.These issues may present related barriers when formulating consumer andindustrial products containing surfactants.

In addition to their frequent use in facilitating emulsification orde-emulsification in various industries and consumer products,surfactants are also commonly employed for promoting foam formation inaqueous fluids. Foaming properties of soaps, detergents, shampoos andsimilar consumer products are familiar examples. Foamed treatment fluidsare also frequently employed in oil and gas production as well. As usedherein, the term “foam” refers to a stabilized dispersion of a largevolume of gas in the form of bubbles of varying sizes in a relativelysmall volume of liquid. The term “foam quality” refers to the percentageof gas in a volume of foam and may be calculated by dividing thequantity (total foam volume−liquid volume) by the total foam volume.Ionic surfactants are among the most commonly used type of surfactantsfor promoting foaming. However, ionic surfactants can lead toincompatibilities with other types of materials, such as divalent ions,and some may be subject to regulatory constraints, especially when usedin large quantities. In addition, ionic surfactants may sometimes affordinconsistent foam performance at higher temperatures.

BRIEF DESCRIPTION OF THE DRAWINGS

The following figures are included to illustrate certain aspects of thepresent disclosure, and should not be viewed as exclusive embodiments.The subject matter disclosed is capable of considerable modifications,alterations, combinations, and equivalents in form and function, withoutdeparting from the scope of this disclosure.

FIGS. 1A-1D show plots of percent emulsification as a function of timefor Terero oil emulsified with Samples A-D, respectively.

FIGS. 2A-2D show plots of percent emulsification as a function of timefor Wolfcamp A oil emulsified with Samples A-D, respectively.

FIGS. 3A-3D show plots of surface tension as a function of concentrationfor Samples A-D, respectively.

FIGS. 4A-4D show plots of percent emulsification as a function of timefor East Texas Hutcheson #2 oil emulsified with Samples E1-E4, F1-F4,G1-G4, and H1-H4.

FIG. 5 shows a plot of percent water emulsification at 60 minutes forSamples E1-E4, F1-F4, G1-G4, and H1-H4.

FIG. 6 shows a bar graph of Hart-DeGeorge Foam Test performance of anexperimental soap formulation and a comparative soap formulation. Theexperimental soap formulation contains a reaction product ofmaltodextrin and lauric acid formed in the presence of cocamidediethanolamine, and the comparative soap formulation contains anequivalent mass of sodium lauryl sulfate, an anionic surfactant commonlyused in soaps and personal care products.

DETAILED DESCRIPTION

The present disclosure generally relates to surfactant technology and,more specifically, compositions having a low surface tension that mayemulsify, de-emulsify, viscosify or foam a fluid. In some emulsionapplications, the compositions may form microemulsions. Variousindustrial and consumer products may be formed from the compositions,including foamed or foamable compositions.

As discussed above, emulsion management may be desirable when producinga hydrocarbon resource from a subterranean formation. In some instances,it may be suitable for an emulsion to be present, such as to promotetransportation of solids to or from a subterranean formation or tochange the wetting characteristics of a surface within a wellbore. Inother instances, it may be advantageous to break an emulsion to allowproduction of a hydrocarbon resource to take place. Surfactants ofvarious types may be used for these purposes, as well as being found ina wide array of industrial and consumer products. Oftentimes,surfactants having vastly different structures are used to promoteemulsification and de-emulsification. Surface tension (interfacialtension) and intrafacial tension values are frequently high for sometypes of surfactants as well, and some may be subject to regulatoryconstraints. In addition, some types of surfactants, particularlyanionic surfactants, may deleteriously interact with components that maybe present in a fluid, such as salts.

Surfactants also may be utilized to promote foaming of a fluid. Inaddition to the familiar presence of foams associated with household andpersonal care products, such as soaps and detergents, foams arefrequently utilized in oil and gas production as a specialty treatmentfluid. When used to promote foaming in these and other applications,surfactants may present some of the same types of issues as thoseencountered when promoting emulsification or de-emulsification. Inaddition, ionic surfactants may lead to inconsistent foam performance incertain instances, especially at higher temperatures and in the presenceof certain metal cations.

The present disclosure provides biopolymer-based compounds that may beproduced with tunable addends (e.g., to adjust hydrophilic-lipophilicbalance (HLB)) to promote emulsification or de-emulsification dependingon how the biopolymer is functionalized, including when combined with asuitable neutral surfactant. Namely, the present disclosure providessaccharide polymers comprising dextran or dextrin compounds that arereacted with fatty acids, preferably under alkaline conditions andoptionally in the presence of the neutral surfactant, to afford reactionproducts having surfactant-modifying properties and unexpectedly lowsurface tension values when present in combination with a suitablesurfactant. Without being limited by theory, the reaction products mayinclude at least one fatty ester of the dextran or dextrin compound,which interact synergistically with the neutral surfactant to afford thelow surface tension values. Components forming the reaction productsindividually tend to raise surface tension values, but once all combinedtogether in a reaction product may surprisingly lower the surfacetension of cocamide diethanolamine (CocoDEA) and similar neutralsurfactants, possibly after further reaction of a primary alcoholfunctionality thereof. Similar neutral surfactants that may function ina like manner may include, but are not limited to, other fatty acidamide alkanolamines, such as those formed from palmitic acid andethanolamine or diethanolamine, for example. Dextrin compounds also haveprimary alcohol functionalities, as well as secondary alcoholfunctionalities, that may undergo reaction with a fatty acid to form areaction product according to the present disclosure. The reactionproducts may be advantageous due to their biological origin, low costand ability to afford low surface tension values when present incombination with a neutral surfactant. Moreover, the chain length of thefatty acid component of the reaction products may aid in tailoring theproperties obtained therefrom, including determining whether emulsifyingor de-emulsifying performance results in a particular circumstance.Reaction products of maltodextrin represent a particularly useful classof dextrin-based reaction products.

In addition, reaction products having a sufficiently highhydrophilic-lipophilic balance (HLB) may promote foaming offormulations, including when combined with one or more suitablesurfactants. The combination of a neutral surfactant and reactionproducts of the present disclosure may promote ready foaming of anaqueous fluid, and may afford a more stable foam than does a comparablemass of ionic surfactant, including cationic, anionic, or zwitterionicsurfactants. A zwitterionic surfactant may optionally be combined withthe reaction products to improve foaming performance relative to thereaction products and a neutral surfactant alone. For example, whencombined with CocoDEA, other fatty acid amide alkanolamines or areaction product thereof, a reaction product formed from maltodextrinand lauric acid may generate a less dense and more stable foam than doesa substantially equivalent amount of sodium lauryl sulfate (sodiumdodecyl sulfate), an anionic surfactant that is commonly used inpersonal care products such as soaps and shampoos. Given the biomoleculenature of the reaction products, foamed or foamable formulationscomprising one or more reaction products of the present disclosure mayrepresent a more environmentally friendly approach for formulating soapsand other personal care products.

In addition to affording foamed or foamable formulations based uponneutral surfactant technology, the reaction products of the presentdisclosure may fully or partially replace more costly surfactants and/orsurfactants subject to government regulations in various industrial orconsumer products. For example, the reaction products of the presentdisclosure may be an effective replacement for ethyoxylated alcoholneutral surfactants. The lowering of surface tension afforded by thereaction products of the present disclosure in combination with aneutral surfactant may be advantageous when replacing a less desirablesurfactant.

Maltodextrins represent an advantageous saccharide polymer for use inthe disclosure herein in terms of their low cost, environmentally benignnature, and the relative ease with which they may be chemically reactedwith fatty acids having a range of chain lengths. Depending on the fattyacid reacted with a maltodextrin, the hydrophobic-lipophilic balance(HLB) of the reaction products may range from about 5 to about 20 ormore, wherein known molecular contributions may be utilized to calculatethe HLB value. Thus, maltodextrin reaction products may be effective forforming emulsions in substantially water-based fluids or substantiallyoil-based fluids, with a particular fatty acid being selected forreaction with maltodextrin based upon the particular conditions and typeof hydrocarbon resource present downhole or needed when formulating agiven product. Likewise, such maltodextrin reaction products may promotefoaming if the HLB is sufficiently large. In addition to the propertyvariation resulting from the fatty acid size, maltodextrins areavailable in a range of oligomer sizes (e.g., 3-20 glucose monomers, oreven up to about 25 glucose monomers), which may allow some furthertailoring of the emulsifying or foaming properties to be realized. Assuch, maltodextrin reaction products may offer numerous advantages and awide range of applicability for use downhole and in other applicationsin which surfactants are commonly used, such as in soaps and otherpersonal care products. Dextran reaction products may offer similaradvantages and features to those of maltodextrin reaction products,including the ability to produce low surface tension values, and beformed and used under similar conditions.

Dextrin compounds suitable for use in the present disclosure maycomprise 2 to about 20 glucose monomers, or even up to about 25 glucosemonomers, linked together with α(1,4) glycosidic bonds. At least aportion of the glucose monomers may form a reaction product upon beingcontacted under suitable conditions with a fatty acid salt, such as asalt of a C₄-C₃₀ fatty acid or a C₄-C₂₀ fatty acid. Without beinglimited by theory, at least a portion of the glucose monomers may reactto form a fatty ester of the dextrin compound in some embodiments,optionally present in combination with unreacted fatty acid salt in anaqueous phase. When formed, an ester reaction product may form at anyhydroxyl group of the dextrin compound, including any combination ofprimary and/or secondary hydroxyl groups. Hydroxyl groups upon theneutral surfactant may undergo a reaction under similar conditions.

Dextran is a saccharide polymer characterized by predominantly α(1,6)glycosidic bonds between adjacent glucose monomers, with a limitednumber of glucose side chains linked to the main polymer backbone viaα(1,3) glycosidic bonds. The α(1,3) glycosidic bonds may introducecrosslinks between adjacent saccharide polymer chains. Depending on thebiological source, the extent of branching and the molecular weight ofdextran may vary considerably, any of which may be utilized in thedisclosure herein. At least a portion of the glucose monomers in dextranmay form a reaction product upon being contacted under suitableconditions with a fatty acid salt, such a salt of a C₄-C₃₀ fatty acid ora C₄-C₂₀ fatty acid. Without being limited by theory, at least a portionof the glucose monomers may react to form a fatty ester of the dextranin some embodiments, optionally present in combination with unreactedfatty acid salt in an aqueous phase. When formed, an ester reactionproduct may form at any hydroxyl group of the dextran.

In some embodiments, reaction products of the present disclosure mayinclude a dextrin compound having 3 to about 20 glucose monomers, oreven up to about 25 glucose monomers, that are covalently linked byα(1,4) glycosidic bonds. Formula 1 below shows the generic structure ofa dextrin compound having only α(1,4) glycosidic bonds between adjacentglucose monomers, wherein variable ‘a’ is a positive integer rangingfrom 1 to about 18, thereby providing a dextrin backbone with 3 to about20 glucose monomers. In the case of a dextrin compound containing up to25 glucose monomers, variable ‘a’ may range from 1 up to about 23. Theterminal glucose unit is shown in its closed form, but may also bepresent in the corresponding reducing sugar form as well.

Other dextrin compounds may contain only α(1,6) glycosidic bonds or amixture of α(1,4) and α(1,6) glycosidic bonds, and such dextrincompounds may also be suitable for use in forming the reaction products.Particularly suitable dextrins may have a molecular weight (e.g., M_(n))in the range of about 1200 to about 1400 or about 1100 to about 1500.

In some or other embodiments, the reaction products may include adextran obtained from any suitable source. The structure of dextran isshown in Formula 2 below, in which the α(1,3) glycosidic bonds are notshown in the interest of clarity. Where they occur, the α(1,3)glycosidic bonds may append a terminal glucose monomer as a side chainto the α(1,6)-linked saccharide polymer backbone, form crosslinksbetween adjacent α(1,6)-linked saccharide polymer backbones, interruptthe α(1,6)-linked saccharide polymer backbone with an α(1,3) glycosidicbond, or any combination thereof. Depending on source, up to about 5% ofthe glucose monomers may be linked by α(1,3) glycosidic bonds. Linkageby α(1,3) glycosidic bonds may occur upon any of the glucose monomers.The numbering of a single glucose monomer is shown in Formula 3 below.

Suitable dextrans may have a molecular weight of about 1200, or about1400, or about 5000 up to about 50,000,000 or about 100,000 up to about20,000,000. As such, variable ‘b’ may range from about 30 to about300,000 depending on the particular dextran selected. Particularlysuitable dextrans may have a molecular weight (e.g., M_(n)) ranging fromabout 1200 to about 1400, or about 1100 to about 1500, or about 100,000to about 1 million, or about 2 million to about 5 million. Anothersuitable dextran may have a molecular weight of about 500,000 and anactivity level of about 9%.

The saccharide polymer may comprise a maltodextrin according to someembodiments of the present disclosure. Maltodextrins may becharacterized in terms of their dextrose equivalent (DE) value. Dextroseequivalent is a measure of the amount of reducing sugars (e.g., glucosemonomers) that are present in a saccharide polymer, particularly adextrin, expressed as a percentage relative to dextrose. Starch, whichis functionally non-reducing, has a defined dextrose equivalent of 0,whereas dextrose itself has a dextrose equivalent of 100. Dextroseequivalent may be calculated by dividing the molecular weight of glucoseby M_(n) and multiplying the result by 100. Higher dextrose equivalentvalues are characteristic of a lower number of covalently linked glucosemonomers (shorter polymer backbone length, thereby providing a higherrelative percentage of terminal reducing sugars). Maltodextrins suitablefor forming a reaction product with one or more fatty acids according tothe disclosure herein may exhibit dextrose equivalent values rangingfrom 3 to about 25 or from 3 to about 20. In more specific embodiments,dextrose equivalent values of the maltodextrins may range from about 4.5to about 7.0, or from about 7.0 to about 10.0, or from about 9.0 toabout 12.0.

Maltodextrins suitable for forming a reaction product may be obtainedfrom hydrolysis or pyrolysis of starch, specifically the amylosecomponent of starch, according to some embodiments. A maltodextrinhaving Formula 1 may be formed by hydrolysis or pyrolysis of amylose,for example. Alternative suitable dextrins may be obtained fromhydrolysis or pyrolysis of the amylopectin component of starch, in whichcase the dextrin may contain α(1,6) glycosidic bonds if the dextrin isobtained through hydrolysis of the amylopectin side chain. Starches fromwhich the dextrins may be subsequently produced may be obtained from anystarch source.

Accordingly, reaction products of the present disclosure may comprise afirst reaction component comprising a saccharide polymer selected from adextran, a dextrin compound, or any combination thereof and a secondreaction component comprising one or more fatty acids. The reactionproducts may be obtained in the presence of water and a hydroxide base.Suitable hydroxide bases may include, for example, alkali metalhydroxides, such as sodium hydroxide, potassium hydroxide, or anycombination thereof. A stoichiometric excess or a stoichiometric deficitof the hydroxide base relative to the one or more fatty acids may bepresent. Optionally, the reaction product may be formed in the presenceof a neutral surfactant.

A molar ratio of fatty acid to glucose monomers in the reaction productmay be about 0.05 or above on a basis ofmoles_(fatty acid):moles_(glucose monomers), or about 0.08 or above on abasis of moles_(fatty acid):moles_(glucose monomers), or about 0.1 orabove on a basis of moles_(fatty acid):moles_(glucose monomers), orabout 0.2 or above on a basis ofmoles_(fatty acid):moles_(glucose monomers), or about 0.3 or above on abasis of moles_(fatty acid):moles_(glucose monomers), or about 0.4 orabove on a basis of moles_(fatty acid):moles_(glucose monomers), orabout 0.5 or above on a basis ofmoles_(fatty acid):moles_(glucose monomers), or about 0.6 or above on abasis of moles_(fatty acid):moles_(glucose monomers), or about 0.7 orabove on a basis of moles_(fatty acid):moles_(glucose monomers), orabout 0.8 or above on a basis ofmoles_(fatty acid):moles_(glucose monomers), or about 0.9 or above on abasis of moles_(fatty acid):moles_(glucose monomers). A maximum ratio offatty acid to dextrin or dextran in the reaction product, based uponglucose monomers, may be about 1.0 in most cases. The foregoing ratiosmay represent a molar ratio of fatty acid reacted with the dextran ordextrin compound. One or more hydroxyl groups per glucose monomer mayundergo a reaction in some cases. At least a portion of the glucosemonomers may remain unfunctionalized. Unreacted carboxylic acids, ifany, may remain in the reaction product as a free carboxylate salt ofthe hydroxide base. As such, reaction products of the present disclosuremay comprise one or more dextrin fatty esters and/or one or more dextranfatty esters, optionally in further combination with a fatty acidcarboxylate (e.g., an alkali metal carboxylate), and a hydroxide base(e.g., an alkali metal hydroxide base). The hydroxide base may bepresent in at least a sufficient molar quantity to react withsubstantially all of the fatty acid that is present to form an alkalimetal carboxylate. The hydroxide base may be neutralized with an acid orremoved through washing, and the reaction products may maintain theirability to afford a low surface tension.

Compositions of the present disclosure may comprise a neutral surfactantand/or a zwitterionic surfactant in combination with the foregoingreaction products. Surprisingly, the reaction products of the presentdisclosure may promote lowering of the surface tension of the neutralsurfactant or zwitterionic surfactant. That is, the reaction product maybe present in an effective concentration to lower the surface tensionrelative to that produced by the neutral surfactant or the zwitterionicsurfactant alone at a substantially similar concentration. Neutralsurfactants may be useful due to their already-low surface tensionvalues. When combined with the saccharide polymer during formation ofthe reaction product, alcohol groups upon a neutral surfactant may forma reaction product, such as with the fatty acid, as well.

Suitable neutral surfactants that may have their surface tension loweredin combination with a reaction product include cocoamide-basedsurfactants such as cocamide diethanolamine, cocamide monoethanolamine,cocamide monoisopropanolamine, cocamide diisopropanolamine, and thelike. Cocamide diethanolamine (CocoDEA) may be a suitable neutralsurfactant for use in the disclosure herein. Other neutral surfactantsthat may be suitable include additional fatty acid amide alkanolamines,such as palmitic acid amide diethanolamine or monoethanolamine. In thecompositions of the present disclosure, such neutral surfactants may bepresent at a concentration of about 20 wt. % or less, or about 10 wt. %or less, or about 5 wt. % or less, such as about 1 wt. % to about 10 wt.%, or about 3 wt. % to about 8 wt. %.

Betaine surfactants are a type of zwitterionic surfactant. Since the netcharge of zwitterionic surfactants is zero, they also may be consideredto constitute neutral surfactants in the disclosure herein. Zwitterionicsurfactants, such as cocamidopropyl betaine, may also be present in thecompositions of the present disclosure in some instances, either aloneor in combination with a neutral surfactant, particularly when producingfoamable formulations comprising the reaction products. Zwitterionicsurfactants may likewise have their surface tension lowered whencombined with the reaction products.

Once formed, the pH of the reaction products disclosed herein may residewithin a range of about 1 to about 14, such as a range of about 1 toabout 5, or about 5 to about 7, or about 7 to about 9, or about 9 toabout 14. Lower surface tension values may be realized as the pHdecreases in some instances. Decreased surface tension may also berealized in the presence of dissolved salt, such as potassium chloride.

Reaction products of the present disclosure, which may include thoseformed through a reaction of one or more fatty acids with dextrincompounds and/or a dextran, may be prepared by a process comprising:heating a saccharide polymer comprising a dextran, a dextrin compound(e.g., comprising 3 to about 20 glucose monomers, or even up to about 25glucose monomers, linked together with α(1,4) glycosidic bonds), or anycombination thereof, a fatty acid and a hydroxide base in water,obtaining a reaction product of the saccharide polymer and the fattyacid in an aqueous phase, and combining a neutral surfactant oroptionally a reaction product thereof, such as a cocamide-basedsurfactant, or a zwitterionic surfactant with the reaction product inthe aqueous phase. The reaction product may be combined with the neutralsurfactant or zwitterionic surfactant in an amount effective to decreasethe surface tension relative to the surfactant alone at a likeconcentration. Any of the reaction products of a dextran or dextrincompounds may constitute a suitable saccharide polymer for formingcompositions having a low surface tension. Heating may be conducted at atemperature of about 100° C. or less, such as at about 50° C. to about80° C., or about 60° C. to about 70° C., or about 50° C. to about 60° C.

The reaction product may be formed in the presence of the neutralsurfactant or zwitterionic surfactant, or the neutral surfactant orzwitterionic surfactant may be combined after formation of the reactionproduct has been completed. For example, the reaction product may beprecipitated and subsequently be redissolved in an aqueous solutioncontaining the neutral surfactant or zwitterionic surfactant. In someembodiments, the reaction products may be formed in the presence of orbe combined with a neutral surfactant due to the low surface tensionvalues that may be obtained. When present during formation of thereaction product, a reaction product of a neutral surfactant havinghydroxyl groups may be formed.

When a neutral surfactant is used, surface tension values for thecompositions may be about 40 dynes/cm or less, or about 38 dynes/cm orless, or about 36 dynes/cm or less, or about 34 dynes/cm or less, orabout 32 dynes/cm or less, or about 30 dynes/cm or less, or about 28dynes/cm or less. The surface tension may be largely governed by theamount of neutral surfactant that is present, with the chosen amount ofneutral surfactant being selected to provide a desired extent ofsurfactancy applicable to a given application. At the chosen amount ofneutral surfactant, the reaction product may be present in an amountsufficient to lower the surface tension in comparison to the surfacetension that would otherwise be obtained for the surfactant alone at asubstantially identical concentration. Corresponding intrafacial tensionvalues for the compositions may be about 10 dynes/cm or less.

In forming the reaction products of the present disclosure, methods ofthe present disclosure may comprise combining the fatty acid, thehydroxide base, and the neutral surfactant and/or zwitterionicsurfactant in water to form a mixture, and heating the mixture until thefatty acid dissolves and a homogeneous mixture forms. Thereafter, themethods may comprise combining the saccharide polymer with thehomogeneous mixture and continuing to heat until the reaction producthas formed to a sufficient degree. The resulting aqueous mixture may beutilized directly in further applications, optionally afterconcentration or dilution, by being further combined with additionalcomponents targeted for a particular formulation. Formulations andproducts in which aqueous mixtures of the reaction products may beutilized are discussed hereinbelow. In some instances, the aqueousmixture may at least partially replace another surfactant in a specificformulation, such as a charged surfactant. In other instances, theaqueous mixture may at least partially replace an ethoxylated alcoholsurfactant in a formulation.

Fatty acids suitable for use in forming reaction products of the presentdisclosure may be selected to afford reaction products having a range ofHLB values, such as HLB values of about 5 to about 20. The fatty acidsmay range in size from about C₄ to about C₃₀, or about C₄ to about C₂₀,or about C₆ to about C₁₈, or about C₈ to about C₂₄. Suitable fatty acidsfor forming a reaction product according to the disclosure herein may bestraight chain or branched, and saturated or unsaturated. Illustrativefatty acids that may be suitable for forming a reaction product of thepresent disclosure include, for example, butyric acid, valeric acid,caproic acid, enanthic acid, caprylic acid, pelabonic acid, capric acid,undecylic acid, lauric acid, tridecylic acid, myristic acid,pentadecylic acid, palmitic acid, margaric acid, stearic acid,nonadecylic acid, arachidic acid, heneicosylic acid, behenic acid,trioscylic acid, lignoceric acid, pentacosylic acid, cerotic acid,carboceric acid, montanic acid, nonacosylic acid, melissic acid,crotonic acid, cervonic acid, linoleic acid, linolelaidic acid,linolenic acid, arachidonic acid, docosatetraenoic acid, myristoleicacid, palmitoleic acid, sappenic acid, vaccenic acid, paullinic acid,oleic acid, pinolenic acid, stearidonic acid, eleostearic acid, elaidicacid, gondoic acid, gadoleic acid, erucic acid, eicosenoic acid,eicosadiencoic acid, eicosatrienoic acid, eicosatetraenoic acid,docosadienoic acid, nervonic acid, mead acid, adrenic acid, the like,and any combination thereof. Lauric acid or a blend of lauric acid andmyristic acid may be one example of a suitable acid. Any branchedvariant of the foregoing fatty acids may also be suitably used to form areaction product of the present disclosure.

Methods of the present disclosure may further comprise inducing foamformation in the aqueous phase after obtaining the reaction producttherein, optionally after further combining the reaction product withwater and/or adding additional components. Inducing foam formation ofthe aqueous phase may take place by agitating the aqueous phase in thepresence of a gas, such as through stirring or blending in the presenceof the gas, bubbling gas through the aqueous phase, or any combinationthereof. The neutral surfactant and/or zwitterionic surfactant may bepresent in combination with the reaction product while forming the foam.

Gases suitable for forming a foam in the presence of the reactionproducts are not believed to be particularly limited. Suitable gases forforming a foam may include, but are not limited to, air, nitrogen,carbon dioxide, helium, natural gas, or any combination thereof. Aerosolpropellants may also be used in some instances.

Foams formed according to the disclosure herein may have a foam qualityof about 10% or above, or about 20% or above, or about 30% or above, orabout 40% or above, or about 50% or above, or about 60% or above, orabout 70% or above, or about 80% or above, or about 90% or above. Theupper limit of the foam quality may be about 99%, or about 95%, or about90%, or about 80%, or about 70%, or about 60% or about 50%.

Foamed or foamable formulations of the present disclosure may comprisean aqueous phase comprising an aqueous carrier fluid, which is describedin more detail hereinafter. Foamed formulations (foams) are compositionsto which a gas has already been introduced and foam bubbles have formed.That is, foamed formulations may comprise a gas, and an aqueous fluidcomprising a composition described herein admixed together with the gasas a plurality of bubbles. Foamable formulations, in contrast, arecompositions suitable for forming a foam once a gas has been introducedthereto, but which have not yet formed foam bubbles.

In addition to the reaction products of the present disclosure, foamedor foamable formulations may further comprise one or more additionalsurfactants, which may be cationic, anionic, zwitterionic, neutral, orany combination thereof. Foamed or foamable formulations may alsocontain additional components found in soaps and other personal careproducts, examples of which will be familiar to persons having ordinaryskill in the art. Additional disclosure directed to industrial andconsumer products, including personal care products and foamed variantsthereof, in which the compositions described herein may be present arediscussed in further detail below.

Reaction products may be provided, sourced, mixed, or stored in solidform or in liquid form. Liquid forms may be disposed in a suitable fluidphase, such as an aqueous phase, which may be emulsified ornon-emulsified depending on particular formulations and intendedapplications. In addition, the aqueous phase may be foamed in someinstances. As used herein, the terms “fluid” and “fluid phase” refer toboth liquids and gels, including solutions, emulsions and suspensions ofthe reaction products, including foams, unless otherwise indicated.Compositions including a reaction product of the present disclosure maycomprise an aqueous carrier fluid. Suitable aqueous carrier fluids mayinclude, for example, fresh water, acidified water, seawater, brine(i.e., a saturated salt solution), or an aqueous salt solution (i.e., anon-saturated salt solution). Water-miscible organic co-solvents such asethanol or ethylene glycol, for example, may be present in combinationwith an aqueous carrier fluid, in some embodiments. Suitable aqueouscarrier fluids may be present while forming the reaction products, or anaqueous carrier fluid may be introduced to the reaction productsfollowing their formation.

Subterranean Treatment Operations

Reaction products of the present disclosure, including those formed frommaltodextrin, other dextrin compounds, or dextran may be formulated as asubterranean treatment fluid. Treatment fluids may be used in a varietyof subterranean treatment operations to facilitate or promote a desiredoutcome within the subterranean formation. As used herein, the term“treatment fluid” refers to any fluid used in a subterranean treatmentoperation in conjunction with achieving a desired function and/or for adesired purpose. Unless otherwise specified, use of the term “treatmentfluid” does not imply any particular action by the treatment fluid or acomponent thereof. Illustrative treatment operations that may befacilitated through use of the reaction products of the presentdisclosure include, without limitation, drilling operations, stimulationoperations, production operations, remediation operations, sand controloperations, and the like, which may include, for example, fracturingoperations, gravel packing operations, acidizing operations, descalingoperations, consolidation operations, workover operations, cleanupoperations, diversion operations, and the like. Any of these treatmentoperations may feature emulsification, de-emulsification, a change insurface wetting characteristics downhole, or any combination thereof.

As used herein, the term “drilling operation” refers to the process offorming a wellbore in a subterranean formation. As used herein, the term“drilling fluid” refers to a fluid used in drilling a wellbore.

As used herein, the term “stimulation operation” refers to an activityconducted within a wellbore to increase production therefrom. As usedherein, the term “stimulation fluid” refers to a fluid used downholeduring a stimulation activity to increase production of a hydrocarbonresource from the subterranean formation. In some instances, stimulationfluids may include a fracturing fluid or an acidizing fluid.

As used herein, the terms “clean-up operation” or “damage controloperation” refer to any operation for removing extraneous material froma wellbore to increase production. As used herein, the terms “clean-upfluid” or “damage control fluid” refer to a fluid used for removing anunwanted material from a wellbore that otherwise blocks flow of adesired fluid therethrough. In one example, a clean-up fluid can be anacidified fluid for removing material formed by one or more perforationtreatments. In another example, a clean-up fluid can be used to remove afilter cake upon the wellbore walls. For example, a reaction product ofthe present disclosure may promote liberation of a hydrocarbon resourcefrom a subterranean formation to promote wellbore cleanup by changingsurface wetting characteristics. In another embodiment, treatment fluidscomprising a reaction product of the present disclosure may beintroduced to a subterranean formation in emulsified form and undergo asubsequent break (de-emulsification) therein to promote a desired actionwithin the subterranean formation. In still other embodiments, thetreatment fluids may promote de-emulsification of a fluid downhole, suchas an emulsified hydrocarbon resource.

As used herein, the term “fracturing operation” refers to a highpressure operation that creates or extends a plurality of flow channelswithin a subterranean formation. As used herein, the term “fracturingfluid” refers to a viscosified fluid used in conjunction with afracturing operation. A plurality of proppant particulates may bepresent in a fracturing fluid to maintain the flow channels created orextended in the fracturing operation in an open state.

As used herein, the term “remediation operation” refers to any operationdesigned to maintain, increase, or restore a specific rate of productionfrom a wellbore, which may include stimulation operations or clean-upoperations. As used herein, the term “remediation fluid” refers to anyfluid used in conjunction with a remediation operation.

As used herein, the term “acidizing operation” refers to any operationdesigned to remove an acid-soluble material from a wellbore, such as anacid-soluble material that comprises at least a portion of thesubterranean formation. As used herein, the term “acidizing fluid”refers to a fluid used during an acidizing operation. Mineral acids,such as hydrochloric acid or hydrobromic acid, or organic acids may bepresent in compositions utilized for acidizing a carbonate formation,whereas hydrofluoric acid may be present in compositions utilized foracidizing a siliceous formation.

As used herein, the term “spotting fluid” refers to a fluid designed forlocalized treatment of a subterranean formation. In one example, aspotting fluid can include a lost circulation material for treatment ofa specific section of the wellbore, such as to seal off fractures in thewellbore and prevent sag. In another example, a spotting fluid caninclude a water control material or material designed to free a stuckpiece of drilling or extraction equipment.

As used herein, the term “completion fluid” refers to a fluid usedduring the completion phase of a wellbore, including cementingcompositions and cementing fluids.

As used herein, the term “cementing fluid” refers to a fluid used duringcementing operations within a wellbore of a well.

Reaction products of the present disclosure may also be used inconjunction with enhanced oil recovery (EOR) operations. When used inconjunction with EOR operations, the reaction products of the presentdisclosure may change surface wetting within a subterranean formation topromote recovery of a hydrocarbon resource therefrom.

In any of the foregoing treatment operations, the treatment fluid may befoamed. Foamed fracturing fluids, for example, may be advantageouscompared to viscosified treatment fluids for delivery of proppantparticulates to a location in a wellbore. When foamed, treatment fluidsmay have a foam quality ranging from about 1% to about 99%.

Reaction products of the present disclosure may be present in any of thetreatment fluids discussed above. Treatment fluids of the presentdisclosure may feature a concentration of the reaction product of about0.1 gallons per thousand gallons (gpt) to about 10 gpt, or about 0.1 gptto about 1 gpt, or about 0.2 gpt to about 0.5 gpt. These concentrationscorrespond to volume/volume percentages ranging from about 0.01% toabout 1%, or from about 0.01% to about 0.1%, or from 0.02% to about0.05%. The chosen concentration may vary depending upon the particularrequirements for a given treatment operation and/or the specificsubterranean conditions that are encountered downhole. In some examples,the reaction product may be present in a concentration effective tolower a surface tension for a neutral surfactant and/or zwitterionicsurfactant also present in the treatment fluid.

Treatment fluids containing the reaction products of the presentdisclosure may optionally further comprise any number of additives thatmay used in the oilfield services industry. Illustrative additives thatmay be present in a treatment fluid in combination with the reactionproducts of the present disclosure include, for example, surfactants,viscosifiers, gelling agents, gel stabilizers, antioxidants, polymerdegradation prevention additives, relative permeability modifiers, scaleinhibitors, corrosion inhibitors, chelating agents, foaming agents,defoaming agents, antifoaming agents, emulsifying agents, de-emulsifyingagents, iron control agents, proppants or other particulates,particulate diverters, salts, acids, fluid loss control additives, gas,catalysts, other clay control agents, dispersants, flocculants,scavengers (e.g., H₂S scavengers, CO₂ scavengers or O₂ scavengers),lubricants, breakers, friction reducers, bridging agents, weightingagents, solubilizers, pH control agents (e.g., buffers), hydrateinhibitors, consolidating agents, bactericides, catalysts, the like, andany combination thereof. Suitable examples of these additives will befamiliar to one having ordinary skill in the art.

Other Products

The compositions of the present disclosure comprising a reaction productof a dextrin compound, a dextran, or any combination thereof with afatty acid may be formulated in a wide range of industrial or consumerproducts in which surfactants may be used. Personal care products mayrepresent a beneficial class of products in which the compositions ofthe present disclosure may be present, given the relative benign natureof the biomolecules present in the compositions disclosed herein.Illustrative industrial and consumer products in which the compositionsmay be present are provided further below.

Adjuvants are compositions that are used in combination with an activesubstance to increase the efficacy or potency of the active substance.In non-limiting examples, the active substance may be a pharmaceuticalcompound, a personal care compound, or an agricultural compound.

The compositions of the present disclosure (e.g., a reaction product ofa dextrin compound or a dextran and a fatty acid, as specified above, incombination with a neutral surfactant or a zwitterionic surfactant) maybe present in adjuvant compositions in which surfactants of varioustypes may be used. The compositions of the disclosure herein may replacea surfactant used in an adjuvant composition or be used in combinationwith a surfactant already present in an adjuvant composition. Within anadjuvant composition, the compositions may be present in an amount ofabout 0.01 wt. % to about 20 wt. % of the adjuvant composition as awhole, or about 0.1 wt. % to about 10 wt. %, or about 1 wt. % to about15 wt. %, or about 5 wt. % to about 20 wt. %.

An active compound may be present in the adjuvant compositions, or anadjuvant composition may be administered separately from an activecompound. When administered separately, the adjuvant compositions may beadministered before or after the active compound.

Examples of suitable additional components that may be present inadjuvant compositions containing a reaction product of the presentdisclosure include, but are not limited to, other surfactants, anti-foamcompounds, particulates, metal oxides (e.g., silica, alumina, titania,zirconia, and the like), electrolytes, salts, organic solvents, wettingagents, dispersants, emulsifying agents, de-emulsifying agents,penetrants, preservatives, colorants, acids, bases, buffers, chelatingagents, viscosifiers, thixotropic agents, stabilizers, film-formingagents, plasticizers, preservatives, antioxidants, and the like,including any combination thereof. Other surfactants that may be presentin the adjuvant compositions are not particularly limited and mayinclude any one or a combination of cationic, anionic, neutral orzwitterionic surfactants.

Foaming agents are compositions that are a stabilized dispersion of alarge volume of gas in the form of bubbles of varying sizes in arelatively small volume of liquid, or compositions that may form a foamupon suitable introduction of gas thereto (foamable formulations).

The compositions of the present disclosure (e.g, a reaction product of adextrin compound or a dextran and a fatty acid, as specified above, incombination with a neutral surfactant or a zwitterionic surfactant,including the combination of a neutral surfactant and a zwitterionicsurfactant in the case of forming a foam) may be present in foamingagents in which surfactants of various types may be used. Thecompositions of the disclosure herein may replace a surfactant used in afoaming agent or be used in combination with a surfactant alreadypresent in a foaming agent. Within a foaming agent, the compositions maybe present in an amount of about 0.01 wt. % to about 20 wt. % of thefoaming agent as a whole, or about 0.1 wt. % to about 10 wt. %, or about1 wt. % to about 15 wt. %, or about 5 wt. % to about 20 wt. %.

Foaming agents may contain any combination of cationic surfactants,anionic surfactants, zwitterionic surfactants, or neutral surfactants.The compositions disclosed herein may be present in a foaming agent incombination with any of cationic surfactants, anionic surfactants,zwitterionic surfactants, neutral surfactants or any two or more ofthese surfactants. Alternately, the compositions disclosed herein mayreplace all or a portion of any one or more of these surfactants in afoaming agent. For example, the compositions of the present disclosuremay replace anionic surfactants used in combination with zwitterionicsurfactants in a foaming agent. That is, the compositions may be presentin a foaming agent in combination with one or more zwitterionicsurfactants. The compositions may replace a sulfosuccinate surfactant orbe used in combination with a sulfosuccinate surfactant in some foamingagent embodiments, for example.

Examples of suitable additional components that may be present infoaming agents containing a reaction product of the present disclosureinclude, but are not limited to, other surfactants, amines (any one or acombination of primary amines, secondary amines, tertiary amines,diethanolamine, triethanolamine, ethoxylated amines and amidoamines),foam boosters such as amine oxides, solvents, water, salts, skinconditioners (e.g., ethylhexylglycerin, hydroxyethylurea, urea,panthenol, glycerin, isopropyl myristate, propylene glycol, tocopherylacetate, and polyquaternium-11), moisturizers, liquefied gases,supercritical gases, acids, bases, salts, buffers, chelating agents, andthe like, including any combination thereof. Suitable examples of theseadditional components will be familiar to one having ordinary skill inthe art. Other surfactants that may be present in the foaming agents arenot particularly limited and may include any one or a combination ofcationic, anionic, neutral or zwitterionic surfactants.

Hard surface cleaners are compositions that may be used to removevarious substances from surfaces like glass, metals, plastics, stone,concrete, and the like. Hard surfaces that may be cleaned with hardsurface cleaners include, for example, windows, countertops, appliances,floors, driveways, toilets, showers and bathtubs, sinks, and the like.Substances removable from these types of hard surfaces and others span awide range and include, but are not limited to, dirt, grease, soap scum,limescale and similar hard water deposits, and the like.

The compositions of the present disclosure (e.g., a reaction product ofa dextrin compound or a dextran and a fatty acid, as specified above, incombination with a neutral surfactant or a zwitterionic surfactant) maybe present in hard surface cleaners in which surfactants of varioustypes may be used. The compositions of the disclosure herein may replacea surfactant used in a hard surface cleaner or be used in combinationwith a surfactant already present in a hard surface cleaner. Within ahard surface cleaner, the compositions may be present in an amount ofabout 0.01 wt. % to about 20 wt. % of the hard surface cleaner as awhole, or about 0.1 wt. % to about 10 wt. %, or about 1 wt. % to about15 wt. %, or about 5 wt. % to about 20 wt. %.

Examples of suitable additional components that may be present in hardsurface cleaners containing a reaction product of the present disclosureinclude, but are not limited to, other surfactants, foaming compounds,anti-foam compounds, salts such as alkali metal carbonates, organicsolvents such as glycols or glycol ethers, wetting agents, dispersants,emulsifying agents, de-emulsifying agents, colorants, acids, bases,buffers, chelating agents, anti-streaking agents, alkanolamines, and thelike, including any combination thereof Other surfactants that may bepresent in the hard surface cleaners are not particularly limited andmay be any one or a combination of cationic, anionic, neutral orzwitterionic surfactants.

Skin creams and lotions are compositions that may moisturize orotherwise improve the appearance of skin. Skin creams and lotions areinclusive of gels formulation for application to the skin, which mayhave a higher viscosity than creams or lotions.

The compositions of the present disclosure (e.g., a reaction product ofa dextrin compound or a dextran and a fatty acid, as specified above, incombination with a neutral surfactant or a zwitterionic surfactant) maybe present in skin creams and lotions in which surfactants may be used.The compositions may replace a surfactant used in a skin cream or lotionor be used in combination with a surfactant already present in a skincream or lotion. Within a skin cream or lotion, the compositions may bepresent in an amount of about 0.01 wt. % to about 20 wt. % of the skincream or lotion as a whole, or about 0.1 wt. % to about 10 wt. %, orabout 1 wt. % to about 15 wt. %, or about 5 wt. % to about 20 wt. %.

Examples of suitable additional components that may be present in skincreams or lotions disclosed herein include, but are not limited to,other surfactants, emulsifers, essential oils, waxes, fats, solvents,viscosifying agents, mono-alcohols, diols, polyols, diol and polyolethers, milk proteins, emollients, humectants, skin conditioners,preservatives, acids, bases, buffers, chelating agents, thickeners,vitamins, lubricants, wrinkle reducers, moisturizers, radical inhibitorsand other antioxidants, Vitamin A, Vitamin E, ceramides, fatty acids,fatty esters, fatty alcohols, hyaluronic acid, sodium pyroglutamic acid,glycerin, aloe vera, fragrances, colorants, preservatives, sunscreens,and the like, including any combination thereof. Other surfactants thatmay be present in the skin creams and lotions are not particularlylimited and may be any one or a combination of cationic, anionic,neutral or zwitterionic surfactants. The reaction products may replaceat least a portion of one or more existing surfactants in a skin creamor lotion or supplement a quantity of one or more existing surfactantsin a skin cream or lotion.

Body washes and shampoos are cleansing compositions formulated forapplication to the skin or hair. Liquid soaps for more generalizedpersonal cleansing are similar in composition to some body washes andshampoos and may be formulated with many of the same components.

The compositions of the present disclosure (e.g., a reaction product ofa dextrin compound or a dextran and a fatty acid, as specified above, incombination with a neutral surfactant or a zwitterionic surfactant) maybe present in body washes, shampoos and liquid soaps in whichsurfactants may be used. The compositions of the disclosure herein mayreplace a surfactant used in a body wash, shampoo, or liquid soap or beused in combination with a surfactant already present in a body wash,shampoo or liquid soap. Within a body wash, shampoo, or liquid soap, thecompositions may be present in an amount of about 0.01 wt. % to about 20wt. % of the body wash, shampoo, or liquid soap as a whole, or about 0.1wt. % to about 10 wt. %, or about 1 wt. % to about 15 wt. %, or about 5wt. % to about 20 wt. %.

Examples of suitable additional components that may be present in bodywashes, shampoos, or liquid soaps disclosed herein include, but are notlimited to, other surfactants, conditioners, amidoamines, fragrances,colorants, essential oils, foaming agents, humectants, fatty acids,fatty esters, fatty alcohols, waxes, biocides, soaps, preservatives,acids, bases, buffers, chelating agents, thickeners, vitamins,pearlizing agents, viscosifying agents, moisturizers, antioxidants,sunscreens, and the like, including any combination thereof.Illustrative examples of body washes, shampoos, and liquid soaps maycomprise water, an effective amount of the compositions, optionally infurther combination with another surfactant, 0-4% pearlizing agent, 0-1%suspension aids, 0-2% fragrance, 0-0.25% chelating agent, 0-1%preservatives, 0-2% colorant and 0-25% conditioner. Other surfactantsthat may be present in the body washes, shampoos, and liquid soaps arenot particularly limited and may be any one or a combination ofcationic, anionic, neutral or zwitterionic surfactants.

Sunscreens are substances that may be applied to the skin to affordprotection from the sun. Sunscreens may be formulated as creams or witha suitable wax base in “stick” format for application to the skin.

The compositions of the present disclosure (e.g., a reaction product ofa dextrin or dextran and a fatty acid, as specified above, incombination with a neutral surfactant or a zwitterionic surfactant) maybe present in sunscreens in which surfactants may be used. Thecompositions of the disclosure herein may replace a surfactant used in asunscreen or be used in combination with a surfactant already present ina sunscreen. Within a sunscreen, the compositions may be present in anamount of about 0.01 wt. % to about 20 wt. % of the sunscreen as awhole, or about 0.1 wt. % to about 10 wt. %, or about 1 wt. % to about15 wt. %, or about 5 wt. % to about 20 wt. %.

Examples of suitable additional components that may be present insunscreens include, but are not limited to, other surfactants,conditioners, titanium dioxide, zinc oxide, organic UV absorbers, filmforming agents, solvents, aerosol propellants, waxes, fats, oils,moisturizers, fragrances, colorants, essential oils, fatty acids, fattyesters, fatty alcohols, preservatives, acids, bases, buffers, chelatingagents, thickeners, insect repellents, skin conditioners, and the like,including any combination thereof. Other surfactants that may be presentin the sunscreens are not particularly limited and may be any one or acombination of cationic, anionic, neutral or zwitterionic surfactants.

Organic UV absorbers that may be present in a sunscreen in combinationwith the compositions include, but are not limited to, para-aminobenzoicacid, avobenzone, cinoxate, dioxybenzone, homosalate, menthylanthranilate, octyl salicylate, oxybenzone, padimate O,phenylbenzimidazole sulfonic acid, sulisobenzone, trolamine salicylate,diethanolamine methoxycinnamate, digalloy trioleate, ethyldihydroxypropyl PABA, glyceryl aminobenzoate, lawsone withdihydroxyacetone, red petrolatum, ethylhexyl triazone, dioctyl butamidotriazone, benzylidene malonate polysiloxane, terephthalylidene dicamphorsulfonic acid, disodium phenyl dibenzimidazole tetrasulfonate,diethylamino hydroxybenzoyl hexyl benzoate, bis diethylaminohydroxybenzoyl benzoate, bis benzoxazoylphenyl ethylhexylimino triazine,drometrizole trisiloxane, methylene bis-benzotriazolyltetramethylbutylphenol, and bis-ethylhexyloxyphenolmethoxyphenyltriazine, 4-methylbenzylidenecamphor, isopentyl4-methoxycinnamate, phenylbenzimidazole sulfonate, 2-hydroxy-4-methoxybenzophenone-5-sulfonate,4-(2-beta-glucopyrano-siloxy)propoxy-2-hydroxybenzophenone, andbis-sodium phenylene-1,4-bis(2-benzimidazyl)-3,3′-5,5′-tetrasulfonate,2-ethylhexyl-p-methoxycinnamate, 4-tert-4′-methoxydibenzoylmethane,octocrylene,2,4-bis-[{4-(2-ethythexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine,methylene bis-benzotriazolyl tetrarnethyl butylphenol,2,4,6-tris-[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine,diethylamino hydroxybenzoyl hexyl benzoate, oxybenzone, and dihydroxydimethoxy benzophenone, and mixtures thereof.

Still other organic UV absorbers that may be suitable for inclusion in asunscreen include, but are not limited to, bis-resorcinyl triazines;benzimidazole derivatives; 4-methylbenzylidene camphor; benzoylpiperazine derivatives; benzoxazole derivatives; diarylbutadienederivatives; phenyl benzotriazole derivatives; benzylidene malonates;TEA-salicylate; imidazoline derivatives; naphthalates; merocyaninederivatives; aminobenzophenone derivatives; dibenzoylmethanederivatives; 3,3-diphenylacrylate derivatives; camphor derivatives;salicylate derivatives; anthranilate derivatives; and benzalmalonatederivatives.

In addition to formulations that are sunscreens alone, the compositionsof the present disclosure may be present in sunscreens that areincorporated into other products such as lotions, cologne, cosmetics,body washes and shampoos, and the like.

Hair gels and hair sprays are formulations that may be used for holdingone's hair in place, or optionally to provide detangling of one's hair.Hair sprays are aerosolized formations, whereas gels are high-viscosityfluids and may be applied by hand.

The compositions of the present disclosure (e.g., a reaction product ofa dextrin or dextran and a fatty acid, as specified above, incombination with a neutral surfactant or a zwitterionic surfactant) maybe present in hair sprays and hair gels in which surfactants may beused. The compositions of the disclosure herein may replace a surfactantused in a hair spray or hair gel or be used in combination with asurfactant already present in a hair spray or hair gel. Within a hairspray or hair gel, the compositions may be present in an amount of about0.01 wt. % to about 20 wt. % of the hair gel or hair spray as a whole,or about 0.1 wt. % to about 10 wt. %, or about 1 wt. % to about 15 wt.%, or about 5 wt. % to about 20 wt. %.

Examples of suitable additional components that may be present in hairsprays or hair gels include, but are not limited to, other surfactants,cellulose-based biopolymers, water-soluble polymers, polyalkyleneglycols, polyalkylene glycol esters, conditioning agents, emollients,humectants, emulsifiers, opacifying agents, thickening agents, foamstabilizers, viscosity builders, sequestrates, antioxidants,antidandruff agents, suspending agents, proteins, fragrances,sunscreens, botanical extracts, essential oils, fatty acids, fattyesters, fatty alcohols, preservatives, acids, bases, buffers, chelatingagents, thickeners, vitamins, waxes, oils, aerosol propellants,polyvinylpyrrolidone, polyvinyl acetate, vinyl acetate-crotonic acidcopolymers, acrylic acid copolymers, plasticizers, alcohols, and thelike, including any combination thereof. Other surfactants that may bepresent in the hair sprays and hair gels are not particularly limitedand may be any one or a combination of cationic, anionic, neutral orzwitterionic surfactants.

One or more examples of a hair spray or hair gel may comprise acomposition of the present disclosure and one or more of cetearylalcohol, behentrimonium chloride, cyclopentasiloxane, dimethicone,ethylhexyl isononanoate, behenyl alcohol, meadowfoam seed oil,cyclohexasiloxane, olive fruit oil, prunus amygdalus dulcis,stearamidopropyl dimethylamine, behentrimonium methosulfate,amodimethicone, panthenol, glycol stearate, ceteth-2,hydroxyethylcellulose, phenoxyethanol, methylparaben, propylparaben,citric acid, mica, titanium dioxide, iron oxide, fragrance, or anycombination thereof.

One or more examples of a hair spray or hair gel may comprise acomposition of the present disclosure and one or more of cyclomethicone,jojoba ester, dimethicone copolyol, nonfat dry milk, soy protein,stearic acid, capric/caprylic stearic triglyceride, jojoba oil, hybridsunflower oil, cetearyl alcohol, glyceryl stearate, PEG-40 stearate,aloe vera gel, acrylates/C₁₀₋₃₀ alkyl acrylate crosspolymer, propyleneglycol, tocopheryl acetate, methylparaben, propylparaben, fragrance, orany combination thereof.

Cosmetics are formulations that may be used for altering or improvingone's physical appearance. Illustrative cosmetics include, but are notlimited to, lipstick, blush, mascara, foundation, eyeliner, and thelike. Forms of cosmetics may include, for example, emulsions, creams,gels, dispersions, sticks, and the like. Suitable emulsions withincosmetics may include oil-in-water or water-in-oil emulsions.

The compositions of the present disclosure (e.g., a reaction product ofa dextrin or dextran and a fatty acid, as specified above, incombination with a neutral surfactant or a zwitterionic surfactant) maybe present in various types of cosmetics in which surfactants may beused. The compositions of the disclosure herein may replace a surfactantused in cosmetic or be used in combination with a surfactant alreadypresent in a cosmetic. Within a cosmetic, the compositions may bepresent in an amount of about 0.01 wt. % to about 20 wt. % of thecosmetic as a whole, or about 0.1 wt. % to about 10 wt. %, or about 1wt. % to about 15 wt. %, or about 5 wt. % to about 20 wt. %.

Examples of suitable additional components that may be present incosmetics include, but are not limited to, other surfactants, perfumes,preservatives, coloring materials, UV absorbers, moisture-retainingagents, emulsifiers, gelling agents, oils, thickening agents, foamstabilizers, viscosity builders, preservatives, sequestrates,antioxidants, suspending agents, proteins, fragrances, sunscreens,botanical extracts, essential oils, fats (e.g., shea butter, mango seedbutter, and cacao seed butter), fatty acids, fatty esters, fattyalcohols, biocides, soaps, preservatives, acids, bases, buffers,chelating agents, thickeners, vitamins, waxes (e.g., myristyl myristate,Camellia sinensis leaf extract, jojoba, sunflower seed, carnauba wax,candelilla wax, and beeswax), and the like, including any combinationthereof. Some examples of components that may be present in cosmeticsmay include, for example, higher fatty alcohols such as cetyl alcohol,stearyl alcohol and behenyl alcohol; higher fatty acid includingcaprylic/capric triglyceride, lauric acid, myristic acid, palmitic acidand stearic acid; hydrocarbons including ceresin; natural oils includingmeadowfoam seed oil, sunflower seed oil, macadamia seed oil, green teaseed oil, ginger oil, ginseng oil, coconut oil, olive oil and camelliaoil; esters including phytosteryl/octyldodecyl lauroyl glutamate,isostearyl isostearate, methylheptyl isostearate, dicaprylyl carbonateand isopropyl palmitate; ethers including dicaprylyl ether; siliconeoils including dimethicone, cyclopentasiloxane, cyclohexasiloxane,phenyltrimethicone, trisiloxane and methyltrimethicone; and hydrocarbonsincluding squalane. Other surfactants that may be present in thecosmetics are not particularly limited and may be any one or acombination of cationic, anionic, neutral or zwitterionic surfactants.Cosmetics of the present disclosure may be formulated in any suitableform including, sticks, creams, powders, gels, and the like.

Deodorants and antiperspirants are formulations that may be utilized forcontrolling body odor. Deodorants and antiperspirants of the presentdisclosure may be formulated in stick form, gel form, powder form oraerosolizable form.

The compositions of the present disclosure (e.g., a reaction product ofa dextrin or dextran and a fatty acid, as specified above, incombination with a neutral surfactant or a zwitterionic surfactant) maybe present in deodorants and antiperspirants in which surfactants may beused. The compositions of the disclosure herein may replace a surfactantused in a deodorant or antiperspirant or be used in combination with asurfactant already present in a deodorant or antiperspirant. Within adeodorant or antiperspirant, the compositions may be present in anamount of about 0.01 wt. % to about 20 wt. % of the deodorant orantiperspirant as a whole, or about 0.1 wt. % to about 10 wt. %, orabout 1 wt. % to about 15 wt. %, or about 5 wt. % to about 20 wt. %.

Examples of suitable additional components that may be present indeodorants or antiperspirants disclosed herein include, but are notlimited to, other surfactants, aluminum salts (e.g., alum, aluminumchloride, aluminum chlorohydrate, aluminum-zirconium compounds,aluminum-zirconium tetrachlorohydrex gly, and aluminum-zirconiumtetrachlorohydrex gly), anti-bacterial agents, parabens, alcohols,propylene glycol, hexamethylenetetramine, acids, bases, buffers,chelating agents, perfumes, preservatives, coloring materials,moisture-absorbing agents (dessicants), emulsifiers, gelling agents,oils, thickening agents, foam stabilizers, viscosity builders,sequestrates, antioxidants, suspending agents, fragrances, essentialoils, fats, fatty acids, fatty esters, fatty alcohols, waxes, and thelike, including any combination thereof. Other surfactants that may bepresent in the deodorants and antiperspirants are not particularlylimited and may be any one or a combination of cationic, anionic,neutral or zwitterionic surfactants. Deodorants and antiperspirants ofthe present disclosure may be formulated in any suitable form including,sticks, creams, powders, gels, and the like.

The compositions of the present disclosure comprising a reaction productof a dextrin compound, a dextran, or any combination thereof with afatty acid may also find exemplary uses and formulations outside thepersonal care space as well. In addition to the oilfield applicationsdescribed above, the compositions of the present disclosure may beincorporated in applications in which metal sequestration from a fluidis needed, such as within froth floatation processes. Froth floatationprocesses may be conducted in various instances, such as mining runoffor waterwater treatment. In such applications, the compositions of thepresent disclosure may replace a surfactant used in froth floatation orbe used in combination with a surfactant already present in frothfloatation process. Within a given froth floatation process, thecompositions may be present in an amount of about 0.01 wt. % to about 20wt. % of a froth floatation fluid as a whole, or about 0.1 wt. % toabout 10 wt. %, or about 1 wt. % to about 15 wt. %, or about 5 wt. % toabout 20 wt. %.

In some examples, the compositions of the present disclosure may beutilized in roughers and cleaner circuits to promote clay dispersion,water conditioning, additive enhancement and/or emulsification of metalsuppressants such as Mn and Fe. Any conventional frothing agent may beutilized in combination with the compositions disclosed herein. Suitablefrothing agents and details concerning frothing agents will be familiarto one having ordinary skill in the art.

Embodiments disclosed herein include:

A. Compositions comprising a saccharide polymer reaction product with afatty acid. The compositions comprise: a reaction product of asaccharide polymer and a fatty acid obtained in the presence of water, ahydroxide base and a neutral surfactant, the saccharide polymercomprising dextran, a dextrin compound, or any combination thereof.

A1. The composition of A, wherein the saccharide polymer comprisesdextran.

A2. The composition of A, wherein the saccharide polymer comprises adextrin compound.

B. Methods for functionalizing a polysaccharide. The methods comprise:heating a saccharide polymer, a fatty acid, a hydroxide base, and aneutral surfactant in water, the saccharide polymer comprising dextran,a dextrin compound, or any combination thereof; and obtaining a reactionproduct of the saccharide polymer and the fatty acid in an aqueousphase.

B1. The method of B, wherein the saccharide polymer comprises dextran.

B2. The method of B, wherein the saccharide polymer comprises a dextrincompound.

C. Subterranean treatment methods. The methods comprise: providing atreatment fluid comprising the composition of A, A1 or A2, andintroducing the treatment fluid into a subterranean formation.

D. Foamable formulations. The foamable formulations comprise thecomposition of A, A1, or A2.

D1. Soaps and detergents comprising the foamable formulations of D.

E. Foamed formulations. The foamed formulations comprise: a gas, and anaqueous fluid comprising the composition of A, A1 or A2 admixed togetherwith the gas to form a plurality of bubbles.

F. Methods for forming a foam. The methods comprise: providing anaqueous fluid comprising the composition of A, A1 or A2, and inducingfoam formation in the aqueous fluid.

Embodiments A, A1, A2, B, B1, B2, C, D, D1, E and F may have one or moreof the following additional elements in any combination.

Element 1: wherein the saccharide polymer comprises a dextrin compoundand the dextrin compound comprises a maltodextrin.

Element 2: wherein the maltodextrin has a dextrose equivalent value ofabout 3 to about 20.

Element 3: wherein the maltodextrin has a dextrose equivalent value ofabout 4.5 to about 7.0.

Element 4: wherein the maltodextrin has a dextrose equivalent value ofabout 9.0 to about 12.0.

Element 5: wherein the fatty acid comprises about 4 to about 30 carbonatoms.

Element 6: wherein the fatty acid comprises at least one fatty acidselected from the group consisting of butyric acid, valeric acid,caproic acid, enanthic acid, caprylic acid, pelabonic acid, capric acid,undecylic acid, lauric acid, tridecylic acid, myristic acid,pentadecylic acid, palmitic acid, margaric acid, stearic acid,nonadecylic acid, arachidic acid, heneicosylic acid, behenic acid,trioscylic acid, lignoceric acid, pentacosylic acid, cerotic acid,carboceric acid, montanic acid, nonacosylic acid, melissic acid,crotonic acid, cervonic acid, linoleic acid, linolelaidic acid,linolenic acid, arachidonic acid, docosatetraenoic acid, myristoleicacid, palmitoleic acid, sappenic acid, vaccenic acid, paullinic acid,oleic acid, pinolenic acid, stearidonic acid, eleostearic acid, elaidicacid, gondoic acid, gadoleic acid, erucic acid, eicosenoic acid,eicosadiencoic acid, eicosatrienoic acid, eicosatetraenoic acid,docosadienoic acid, nervonic acid, mead acid, adrenic acid, and anycombination thereof.

Element 7: wherein the neutral surfactant comprises cocamidediethanolamine.

Element 8: wherein a molar ratio of fatty acid to dextrin in thereaction product is about 0.2 or above on a basis ofmoles_(fatty acid):moles_(glucose monomers).

Element 8A: wherein a molar ratio of fatty acid to dextrin in thereaction product is about 0.05 or above on a basis ofmoles_(fatty acid):moles_(glucose monomers).

Element 9: wherein a molar ratio of fatty acid to dextrin in thereaction product is about 0.35 or above on a basis ofmoles_(fatty acid):moles_(glucose monomers).

Element 10: wherein the treatment fluid is emulsified when introducedinto the subterranean formation or becomes emulsified within thesubterranean formation.

Element 11: wherein the treatment fluid comprises a water-in-oilemulsion.

Element 12: wherein the treatment fluid comprises an oil-in-wateremulsion.

Element 13: wherein the treatment fluid comprises a microemulsion whenintroduced to the subterranean formation.

Element 14: wherein the treatment fluid promotes enhanced oil recoverywithin the subterranean formation.

Element 14A: wherein the treatment fluid is foamed.

Element 15: wherein the method further comprises combining the fattyacid, the hydroxide base, and the neutral surfactant in the water toform a mixture, heating the mixture until the fatty acid dissolves and ahomogeneous mixture forms, and combining the saccharide polymer with thehomogeneous mixture.

Element 15A: wherein the method further comprises agitating the aqueousphase to form a foam.

Element 16: wherein a foamable formulation comprises the composition.

Element 17: wherein the foamable formulation comprises a soap.

Element 18: wherein inducing foam formation comprises agitating theaqueous fluid to introduce gas thereto.

By way of non-limiting example, exemplary combinations applicable to A,A1, A2, B, B1, B2, C, D1, E and F include, but are not limited to: 1,and 2, 3 or 4; 5 or 6, and 2, 3 or 4; 1 and 7; 1, and 8 or 9; 2, 3 or 4,and 5 or 6; 2, 3 or 4, and 7; 2, 3 or 4, and 8 or 9; 5 or 6, and 7; 5 or6, and 8 or 9; and 7, and 8 or 9. Any of the foregoing may be in furthercombination with one or more of 10-18.

Additional embodiments disclosed herein include:

A′. Compositions comprising a saccharide polymer reaction product with afatty acid. The compositions comprise: a neutral surfactant or areaction product thereof, and a reaction product of a saccharide polymerand a fatty acid, the saccharide polymer comprising a dextran, a dextrincompound, or any combination thereof. The reaction product is present ata concentration effective to lower a surface tension of the neutralsurfactant.

A1′. The composition of A′, wherein the saccharide polymer comprisesdextran.

A2′. The composition of A′, wherein the saccharide polymer comprises adextrin compound, preferably maltodextrin.

B′. Methods for functionalizing a polysaccharide. The methods comprise:heating a saccharide polymer, a fatty acid, and a hydroxide base inwater, the saccharide polymer comprising dextran, a dextrin compound, orany combination thereof; obtaining a reaction product of the saccharidepolymer and the fatty acid in an aqueous phase; and combining a neutralsurfactant or a reaction product thereof with the reaction product ofthe saccharide polymer and the fatty acid in the aqueous phase.

B1′. The method of B′, wherein the saccharide polymer comprises adextran.

B2′. The method of B′, wherein the saccharide polymer comprises adextrin compound, such as maltodextrin.

C′. Subterranean treatment methods. The methods comprise: providing atreatment fluid comprising the composition of A′, A1′ or A2′, andintroducing the treatment fluid into a subterranean formation.

D′. Foamable formulations. The foamable formulations comprise thecomposition of A′, A1′, or A2′.

D1′. Soaps and detergents comprising the foamable formulations of D′.

E′. Foamed formulations. The foamed formulations comprise: a gas, and anaqueous fluid the composition of A′, A1′ or A2′ admixed together withthe gas to form a plurality of bubbles.

F′. Methods for forming a foam. The methods comprise: providing anaqueous fluid comprising the composition of A′, A1′ or A2′, and inducingfoam formation in the aqueous fluid.

G′. Personal care products comprising the reaction product of A′, A1′ orA2′.

H′. Compositions comprising a neutral surfactant, a hydroxide base, asaccharide polymer, and a fatty acid. The saccharide polymer comprises adextran, a dextrin compound, or any combination thereof.

Embodiments A′, A1′, A2′, B′, B1′, B2′, C′, D′, D1′, E′, F′, G′ and H′may have one or more of the following additional elements in anycombination.

Element 1′: wherein the saccharide polymer comprises a dextrin compoundand the dextrin compound comprises a maltodextrin.

Element 2′: wherein the maltodextrin has a dextrose equivalent value ofabout 3 to about 20.

Element 3′: wherein the maltodextrin has a dextrose equivalent value ofabout 4.5 to about 7.0.

Element 4′: wherein the maltodextrin has a dextrose equivalent value ofabout 9.0 to about 12.0.

Element 5′: wherein the fatty acid comprises about 4 to about 30 carbonatoms.

Element 6′: wherein the fatty acid comprises at least one fatty acidselected from the group consisting of butyric acid, valeric acid,caproic acid, enanthic acid, caprylic acid, pelabonic acid, capric acid,undecylic acid, lauric acid, tridecylic acid, myristic acid,pentadecylic acid, palmitic acid, margaric acid, stearic acid,nonadecylic acid, arachidic acid, heneicosylic acid, behenic acid,trioscylic acid, lignoceric acid, pentacosylic acid, cerotic acid,carboceric acid, montanic acid, nonacosylic acid, melissic acid,crotonic acid, cervonic acid, linoleic acid, linolelaidic acid,linolenic acid, arachidonic acid, docosatetraenoic acid, myristoleicacid, palmitoleic acid, sappenic acid, vaccenic acid, paullinic acid,oleic acid, pinolenic acid, stearidonic acid, eleostearic acid, elaidicacid, gondoic acid, gadoleic acid, erucic acid, eicosenoic acid,eicosadiencoic acid, eicosatrienoic acid, eicosatetraenoic acid,docosadienoic acid, nervonic acid, mead acid, adrenic acid, and anycombination thereof.

Element 7′: wherein the neutral surfactant comprises cocamidediethanolamine or a reaction product thereof, or wherein the neutralsurfactant comprises cocamide diethanolamine.

Element 7A′: wherein the reaction product is formed in the presence ofthe neutral surfactant.

Element 8′: wherein a molar ratio of fatty acid to dextrin in thereaction product is about 0.2 or above on a basis ofmoles_(fatty acid):moles_(glucose monomers).

Element 8A′: wherein a molar ratio of fatty acid to dextrin in thereaction product is about 0.05 or above on a basis ofmoles_(fatty acid):moles_(glucose monomers).

Element 9′: wherein a molar ratio of fatty acid to dextrin in thereaction product is about 0.35 or above on a basis ofmoles_(fatty acid):moles_(glucose monomers).

Element 10′: wherein the reaction product of the saccharide polymer isobtained in the presence of water and a hydroxide base.

Element 11′: wherein the reaction product of the saccharide polymercomprise a fatty ester reaction product.

Element 12′: wherein the treatment fluid is emulsified when introducedinto the subterranean formation or becomes emulsified within thesubterranean formation.

Element 13′: wherein the treatment fluid comprises a water-in-oilemulsion.

Element 14′: wherein the treatment fluid comprises an oil-in-wateremulsion.

Element 15′: wherein the treatment fluid comprises a microemulsion whenintroduced to the subterranean formation.

Element 16′: wherein the treatment fluid promotes enhanced oil recoverywithin the subterranean formation.

Element 16A′: wherein the treatment fluid is foamed.

Element 17′: wherein the method further comprises combining the fattyacid, the hydroxide base, and the neutral surfactant in the water toform a mixture, heating the mixture until the fatty acid dissolves and ahomogeneous mixture forms, and combining the saccharide polymer with thehomogeneous mixture.

Element 18A′: wherein the method further comprises agitating the aqueousphase to form a foam.

Element 19′: wherein a foamable formulation comprises the composition.

Element 20′: wherein the foamable formulation comprises a soap.

Element 21′: wherein inducing foam formation comprises agitating theaqueous fluid to introduce gas thereto.

By way of non-limiting example, exemplary combinations applicable to A′,A1′, A2′, B′, B1′, B2′, C′, D′, D1′, E′, F′ and G′ include, but are notlimited to: 1′, and 2′, 3′ or 4′; 5′ or 6′, and 2′, 3′ or 4′; 1′ and 7′or 7A′; 1′, and 8′ or 9′; 2′, 3′ or 4′, and 5′ or 6′; 2′, 3′ or 4′, and7′ or 7A′; 2′, 3′ or 4′, and 8′ or 9′; 5′ or 6′, and 7′ or 7A′; 5′ or6′, and 8′ or 9′; and 7′ or 7A′, and 8′ or 9′. Any of the foregoing maybe in further combination with one or more of 10′-21′.

To facilitate a better understanding of the disclosure herein, thefollowing examples of various representative embodiments are given. Inno way should the following examples be read to limit, or to define, thescope of the invention.

EXAMPLES

Comparative Example 1: Acid-Catalyzed Synthesis of Maltodextrin withLauric Acid. A solution containing 10 wt. % maltodextrin (MALTRIN M100,DE=9.0-12.0, 30% active solution) and 6.18 wt. % lauric acid wasprepared in DMSO. Five drops of phosphoric acid were added, and thereaction mixture was heated at 110° C. for 3 hours. The reaction productwas precipitated by adding 3 volumes of isopropyl alcohol, and a whiteprecipitate was collected by decantation and dried. The product wascharacterized by FTIR and ¹H NMR. The spectral characterization wasconsistent with conversion of maltodextrin into a reaction product.

For surface tension measurements (Table 2), the isolated reactionproduct was redissolved at a concentration of 13.17 wt. % in thepresence of 5 wt. % cocamide diethanolamine (CocoDEA) and 6 wt. % sodiumdodecylbenzene sulfonate (SDDBS).

Comparative Example 2: Acid Chloride-Based Reaction of Maltodextrin. Asolution containing 10 wt. % maltodextrin (MALTRIN M100, DE=9.0-12.0,30% active solution) and 6.75 wt. % lauroyl chloride was prepared informamide. A few drops of phosphoric acid were added, and the reactionmixture was heated at 105° C. for 2 hours. The reaction product wasprecipitated by adding 3 volumes of isopropyl alcohol, and an ambertar-like fluid was obtained. The product was characterized by FTIR and¹H NMR. The spectral characterization was consistent with conversion ofmaltodextrin into a reaction product.

For surface tension measurements (Table 2), the isolated reactionproduct was redissolved at a concentration of 13.17 wt. % in thepresence of 5 wt. % cocamide diethanolamine (CocoDEA) and 6 wt. % sodiumdodecylbenzene sulfonate (SDDBS).

Example 1A: General Procedure for Preparation of Reaction Products ofMaltodextrin Under Basic Conditions. 296.25 g water, 25.00 g cocamidediethanolamine (CocoDEA), and 10.00 g KOH (45% active solution) werecombined. The reaction mixture was mechanically stirred and heated to65° C. Thereafter, 18.75 g fatty acid and 150.0 g maltodextrin (MALTRINM100, Grain Processing Corporation, Muscatine, Iowa; DE=9.0-12.0) as a30% active solution were added to the reaction mixture. Once themaltodextrin dissolved, heating was discontinued and stirring wasconducted until the reaction mixture reached room temperature. Reactionproducts were used without further processing below. Table 1A shows themaltodextrin reaction products synthesized as above and tested in thesubsequent examples. Caprylic acid is synonymous with octanoic acid,lauric acid is synonymous with dodecanoic acid, and stearic acid issynonymous with octadecanoic acid.

TABLE 1A Molar Ratio Fatty Acid:Maltodextrin Sample Fatty Acid (asGlucose Monomer) A Butyric Acid 0.77 B Caprylic Acid 0.47 C Lauric Acid0.34 D Stearic Acid 0.24The general synthetic procedure was followed for all but Sample A. ForSample A, 27.5 g KOH (45% active) and 278.75 g water were used, and theother reaction parameters remained the same. The calculated molar ratiosassume that the entirety of the maltodextrin has the molecular weight ofglucose (180.16 g/mol) less the molecular weight of water (18.02g/mol)=162.14 g/mol.

Example 1B: Alternative Procedure for Preparation of Reaction Productsof Maltodextrin Under Basic Conditions. A solution containing 10 wt. %maltodextrin (MALTRIN M100, DE=9.0-12.0, 30% active solution), 6.18 wt.% lauric acid, and 1.73 wt. % KOH was prepared in water. The reactionmixture was then heated at 65° C. for 30 minutes. The reaction productwas precipitated by adding 3 volumes of isopropyl alcohol, and a whiteprecipitate was collected by decantation and dried. The product wascharacterized by FTIR and ¹H NMR. The spectral characterization wasconsistent with conversion of maltodextrin into a reaction product.Other fatty acids may be reacted similarly.

For surface tension measurements (Table 2), the isolated reactionproduct was redissolved at a concentration of 13.17 wt. % in thepresence of 5 wt. % cocamide diethanolamine (CocoDEA) and 6 wt. % sodiumdodecylbenzene sulfonate (SDDBS). As shown in Table 2, similar surfacetension performance was realized between the reaction products ofExample 1A and Comparative Examples 1 and 2.

Example 2: General Procedure for Preparation of Reaction Products ofDextran Under Basic Conditions. Reaction products were formed fromdextran in a similar manner to that described above for maltodextrin.The dextran had a molecular weight of 500,000 and an activity level of9% within a solution thereof. Table 1B shows the dextran reactionproducts synthesized as above and tested in the subsequent examples.Caprylic acid is synonymous with octanoic acid, lauric acid issynonymous with dodecanoic acid, palmitic acid is synonymous withhexadecanoic acid, and stearic acid is synonymous with octadecanoicacid.

TABLE 1B Weight Ratio Fatty Molar Ratio Acid:Weight Fatty Acid:Dextran(as Sample Fatty Acid Dextran Glucose Monomer) E1 Caprylic Acid  1:100.11 E2 Caprylic Acid 1:5 0.22 E3 Caprylic Acid 1:2 0.57 E4 CaprylicAcid 1:1 1.13 F1 Lauric Acid  1:10 0.081 F2 Lauric Acid 1:5 0.16 F3Lauric Acid 1:2 0.41 F4 Lauric Acid 1:1 0.81 G1 Palmitic Acid  1:100.063 G2 Palmitic Acid 1:5 0.13 G3 Palmitic Acid 1:2 0.32 G4 PalmiticAcid 1:1 0.63 H1 Stearic Acid  1:10 0.057 H2 Stearic Acid 1:5 0.11 H3Stearic Acid 1:2 0.28 H4 Stearic Acid 1:1 0.57

Characterization of Comparative Examples 1 and 2 in Relation to Example1B. Table 2 summarizes the surface tension values for the reactionproducts of Comparative Examples 1 and 2 and the reaction product ofExample 1B (alternative preparation under basic conditions) at aconcentration of 1 gpt (gallons per thousand gallons), in comparison tocontrol samples containing 5 wt. % CocoDEA or 5 wt. % CocoDEA/6 wt. %SDDBS. Surface tension (ST) measurements were made using a BolinScientific Tensiometer at room temperature. Intrafacial tension (IFT)measurements were performed using a hook needle syringe to form a dropof oil in water.

TABLE 2 Surface Tension at 1 gpt Entry Sample (dynes/cm) 1 Control 31.26(5 wt. % CocoDEA/ 6 wt. % SDDBS) 2 Control 34.49 (5 wt. % CocoDEA) 3Comparative 31.77 Example 1 4 Comparative 31.48 Example 2 5 Example 1B31.51The control samples and comparative/experimental samples containedidentical concentrations of CocoDEA or CocoDEA/SDDBS. As shown, thereaction product prepared under basic conditions (Entry 5) affordedsimilar performance to that obtained under acidic conditions (Entries 3and 4). In each case, the surface tension was similar to that of thesurfactant-only CocoDEA/SDDBS control (Entry 1). The surface tensionvalues decreased by about 10% relative to a CocoDEA-only control (Entry2). This surprising result is further elaborated upon below.

Emulsion Performance of Dextrin Reaction Products. Each reaction productprepared as above in Example 1A was formulated at 0.5 gpt (gallons perthousand gallons) and 1 gpt and combined with Terero oil or Wolfcamp AOil. Terero oil is an emulsifying oil, and Wolfcamp A oil is anon-emulsifying oil. The mixture of each oil was then emulsified and theextent of emulsification was followed as a function of time incomparison to a blank. The blank comprised each oil without anyadditional emulsifiers. Emulsification was performed at room temperatureby shaking 50 mL of sample and 50 mL of oil by hand for 60 seconds at arate of about 2 shakes per second. The emulsions were immediately pouredinto a graduated cylinder and time-lapse photography was used to recordthe level of the water layer, the oil layer, and the remaining emulsionlayer. For Wolfcamp A oil, the oil layer and the water layer wereassumed equal, since the oil layer was difficult to differentiate fromthe emulsion layer. FIGS. 1A-1D show plots of percent emulsification asa function of time for Terero oil emulsified with Samples A-D,respectively. FIGS. 2A-2D show plots of percent emulsification as afunction of time for Wolfcamp A oil emulsified with Samples A-D,respectively.

Both oils were initially emulsified in the presence of the maltodextrinreaction products, but the emulsions broke over time, albeit atdifferent rates. Terero oil usually changed its emulsification behavioronly slightly in the presence of the reaction products formed fromcarboxylic acids having varying chain lengths. With the non-emulsifyingWolfcamp A oil, in contrast, the maltodextrin reaction productssometimes afforded faster emulsion breaking than did the control. Theresults suggest that the maltodextrin reaction products, particularlythe specific fatty acid used for functionalization and the amount ofreaction product present, may alter the break properties of thenon-emulsifying Wolfcamp oil itself to varying extents. The differingperformance may arise from variation of the hydrophilic-lipophilicbalance. Moreover, the break properties may differ from that of CocoDEAalone, which afforded a near-complete break of Wolfcamp oil within about30 minutes at 1 gpt (data not shown).

Fluid Properties of Dextrin Reaction Products. Critical micelleconcentration (CMC) measurements and surface tension (ST) measurementswere made using a Bolin Scientific Tensiometer at room temperature.FIGS. 3A-3D show plots of surface tension as a function of concentrationfor Samples A-D, respectively. As shown, Samples B and C reached a CMCat a reaction product concentration of about 0.5 gpt. The surfacetension at the CMC was approximately 30 dynes/cm or slightly below.Samples A and D, in contrast, trended toward lower surface tensionvalues, albeit at higher CMCs. As such, the emulsion performancemeasurements above were performed above the CMC for at least Samples Band C. The surface tension was slightly higher for 0.2 wt. % KClcompared to that obtained with tap water.

The surface tension performance of individual components of the reactionmixture used to produce Sample C were also compared against that of thereaction product itself. Measurements were made at 1 gpt and 2 gpt, asspecified in Table 3 below.

TABLE 3 ST at 1 gpt ST at 2 gpt Entry Component (dynes/cm) (dynes/cm) 1maltodextrin (30% active 73.03 72.85 solution) 2 maltodextrin (30%active n/d 77.39 solution), 1.7% KOH (45% active solution) and 6.18%lauric acid (heated as above) 3 10% maltodextrin (30% 49.23 35.89 activesolution), 5% CocoDEA neutral surfactant solution (heated as above) 4 5%CocoDEA neutral 34.49 31.93 surfactant solution (heated as above) 5 5%CocoDEA neutral 36.73 35.00 surfactant solution containing 2% KOH (45%active solution) (heated as above) 6 5% CocoDEA neutral 39.88 32.99surfactant solution containing 2.47% lauric acid (heated as above) 7 5%CocoDEA neutral 36.52 30.40 surfactant solution containing 2% KOH (45%active solution) and 3.75% lauric acid (heated as above) 8 Sample C28.84 28.59As shown, the maltodextrin itself (Entry 1) afforded a very high surfacetension in comparison to Sample C (Entry 8). In the absence of CocoDEA,the surface tension remained very high even when other components usedto form the reaction product were present (Entry 2). 5 wt. % CocoDEAafforded a much lower surface tension (Entry 4), which increased in thepresence of maltodextrin (Entry 3). When other components used to formthe reaction mixture (except maltodextrin) were combined with 5 wt. %CocoDEA, the surface tension increased slightly (Entries 4-7) relativeto the reaction product. In contrast, when all reaction components werepresent together in Sample C (Entry 8), the surface tension was lowerthan any other tested combination of reaction components. The decreasedsurface tension realized in the presence of the maltodextrin reactionproduct is particularly surprising, given that maltodextrin by itselfincreased the surface tension (Entries 3 and 4).

Tables 4 and 5 show the surface tension performance of Sample C at 1 gptin water and CaCl₂)/water, respectively, at various pH values or CaCl₂)concentrations. The surface tension of Sample C slightly decreasedfurther at more acidic pH values.

TABLE 4 pH Surface Tension (H₂O) (dynes/cm)  1 25.05  4 27.11  7 28.2510 28.25 14 28.64

TABLE 5 CaCl₂ Surface Tension (wt. %) (dynes/cm) 0.2 28.06 2 29.27 1027.17

Intrafacial tension (IFT) measurements were performed using a hookneedle syringe to form a drop of oil in water. The measurements weremade using tap water and Wolfcamp A oil and were evaluated after 61hours of equilibration. Table 6 below summarizes the IFT performance ofSample C.

TABLE 6 Concentration IFT (gpt) (dynes/cm) 0.5 8.57 1 7.51 2 5.48

Emulsion Performance of Dextran Reaction Products. Each reaction productprepared as above was formulated at 1 gpt and combined with East TexasHutchison oil #2. Each oil mixture was then emulsified, and the extentof emulsification was followed as a function of time in comparison to ablank. The blank comprised the oil without any additional emulsifiers.Emulsification was performed at room temperature by shaking 50 mL ofsample and 50 mL of oil by hand for 60 seconds at a rate of about 2shakes per second. The emulsions were immediately poured into agraduated cylinder and time-lapse photography was used to record thelevel of the water layer, the oil layer, and the remaining emulsionlayer. FIGS. 4A-4D show plots of percent emulsification as a function oftime for East Texas Hutchison #2 oil emulsified with Samples E1-E4,F1-F4, G1-G4 and H1-H4, respectively.

FIG. 5 shows a plot of percentage of de-emulsified water present after60 minutes for each dextran reaction product at various weight ratios offatty acid:dextran. As shown, the various dextran reaction productscould promote emulsification or de-emulsification depending on theamount of fatty acid that was reacted with a given quantity of dextran.Series E samples (caprylic acid) afforded minimal emulsification. SeriesF samples (lauric acid) provided strong emulsification at weight ratiosof 1:10 and 1:5, but emulsification decreased considerably at lowerfatty acid loading. At weight ratios of 1:1 and 1:2 caprylic acid andlauric acid afforded little emulsification, but some degree ofemulsification still occurred for palmitic and stearic acid (Series Gand Series H samples) at these weight ratios. Overall, the strongestemulsification effects were observed at a weight ratio of 1:5 for all ofthe fatty acids except for caprylic acid (Series E samples).

Surface Tension of Dextran Reaction Products. The surface tensionperformance of the dextran reaction products was measured at 1 gpt and 2gpt, as specified in Table 7 below.

TABLE 7 ST at 1 gpt ST at 2 gpt Sample (dynes/cm) (dynes/cm) E1 34.6130.25 E2 34.07 29.15 E3 32.39 28.87 E4 31.95 29.00 F1 30.49 28.75 F229.93 27.93 F3 31.34 27.65 F4 68.20 54.71 G1 33.82 28.25 G2 28.77 27.46G3 31.51 28.53 G4 45.76 38.04 H1 34.66 28.75 H2 33.06 28.27 H3 38.0732.13 H4 49.97 40.98As shown, all of the dextran reaction products were capable of loweringthe surface tension of CocoDEA, at least at some concentrations andfatty acid loadings, in a manner similar to that provided by themaltodextrin reaction products described above. At the highest fattyacid loadings (samples F4, G4 and H4), the ability to lower the surfacetension decreased considerably. Thus, the surface tension was tunabledepending on the molecular weight of the fatty acid and the extent offatty acid loading.

Example 3: Substitution of CocoDEA with Betaine Surfactant. Sample C′was prepared in the same manner as Sample C above using the procedure ofExample 1A and similar reagent proportions, except substituting abetaine (zwitterionic) surfactant (SOPALEX 360 BET) for CocoDEA andconducting the reaction at 50° C. Table 8 summarizes the surface tensionof the reaction product in comparison to the betaine surfactant alone.

TABLE 8 ST at 1 gpt ST at 2 gpt Sample (dynes/cm) (dynes/cm)Zwitterionic 71.04 64.9 Surfactant Sample C′ 66.27 55.55Substitution of the betaine surfactant for the neutral surfactantCocoDEA afforded high surface tension values at each testedconcentration. The betaine surfactant by itself afforded relatively highsurface tension values. Surprisingly, the reaction product was operableto decrease the surface tension somewhat in comparison to the betainesurfactant alone.

Example 4: Substitution of CocoDEA with Ethoxylated Alcohol NeutralSurfactant. Sample C″ was prepared in the same manner as Sample C aboveusing the procedure of Example 1A and similar reagent proportions,except substituting an ethoxylated alcohol neutral surfactant (Tomadol1-9) for CocoDEA and conducting the reaction at 50° C. Table 9summarizes the surface tension of the reaction product in comparison tothe ethoxylated alcohol surfactant alone.

TABLE 9 ST at 1 gpt ST at 2 gpt Sample (dynes/cm) (dynes/cm) Ethoxylated46.6 39.5 alcohol surfactant Sample C″ 47.4 41.9The ethoxylated alcohol surfactant afforded much higher surface tensionvalues at each tested concentration than did a like concentration ofCocoDEA. The reaction product in combination with the ethoxylatedalcohol surfactant afforded a similar surface tension to that of theethoxylated alcohol surfactant alone.

Example 5: Decreased CocoDEA Concentration. Sample C′″ was prepared inthe same manner as Sample C above using the procedure of Example 1A andsimilar reagent proportions, except the CocoDEA concentration waslowered to one-fifth the concentration used above (i.e., 1 wt. %). Table10 summarizes the surface tension of the reaction product in comparisonto the reduced-concentration CocoDEA surfactant solution alone.

TABLE 10 ST at 1 gpt ST at 2 gpt Sample (dynes/cm) (dynes/cm) CocoDEA at71.96 67.87 ⅕ concentration Sample C″ 65.84 59.05Lowering the CocoDEA concentration significantly increased the surfacetension values. Even though the surface tension was considerably higherthan when 5 wt. % CocoDEA was present, the reaction product stilldecreased the surface tension in comparison to CocoDEA itself.

Foaming Performance of Dextrin Reaction Products. Sample 1C (reactionproduct of maltodextrin and lauric acid) was processed into a soapformulation having the following composition: 61.1% wt. % deionizedwater, 20.9 wt. % maltodextrin/lauric acid reaction product (combined asaqueous mixture prepared as above), 7.5 wt. % cocamidopropyl betaine,0.5 wt. % glycerin, and 10.0 wt. % SOPALTERIC CS (sodiumcocoamphohydroxypropylsulfonate, Southern Chemical and Textile). Acomparative soap formulation having the following composition wasprepared for side-by-side evaluation of foaming performance: 20 wt. % ofa 30 wt. % sodium lauryl sulfate solution in water, 5 wt. %cocoamidopropyl betaine, 0.5 wt. % glycerin, 0.8 wt. % NaCl and balancedeionized water. The soap formulations contained approximatelyequivalent amounts of the maltodextrin/lauric acid reaction product andsodium lauryl sulfate.

Foaming performance of the experimental soap formulation in comparisonto the comparative soap formulation was assayed using the Hart-DeGeorgeFoam Test. In brief, the Hart-DeGeorge Foam Test utilizes a wire screenplaced between a funnel and a graduated cylinder. A set volume of afoamed mixture is then introduced into the funnel, and the time requiredfor the wire screen (850 μm mesh size) to be exposed is measured. Theliquid level in the graduated cylinder is also measured at varioustimes. Lower density foams are thus characterized by longer timesrequired to expose the wire screen, and lower amounts of liquidcollected in the graduated cylinder are indicative of a more stablefoam.

To conduct Hart-DeGeorge Foam Tests with the experimental andcomparative soap formulations, 1% active solutions of each soapformulation were prepared in separate 200 mL quantities of deionizedwater (soft water) at 25° C. The solutions were then blended at highspeed in a blender for 1 minute. At the completion of blending, theresulting foam was transferred to the funnel. The time required for thewire mesh to be exposed was measured. In addition, the liquid level inthe graduated cylinder was recorded at 1, 2, 3, 4, 5 and 14 minutes.Table 11 summarizes the Hart-DeGeorge Foam Test performance of theexperimental and comparative soap formulations.

TABLE 11 Comparative Soap Experimental Soap Formulation Formulation WireTime (s) 98 91 Liquid Volume-1 min. (mL) 1 1 Liquid Volume-2 min. (mL) 11 Liquid Volume-3 min. (mL) 1 1 Liquid Volume-4 min. (mL) 25 1 LiquidVolume-5 min. (mL) 30 1 Liquid Volume-14 min. (mL) 125 105

The wire time data and liquid volume data is plotted in the bar graphshown in FIG. 6. As shown, the experimental and comparative soapformulations afforded similar wire time performance at substantiallyequivalent surfactant concentrations, thereby indicating a similar foamdensity. The experimental soap formulation, in contrast, afforded asuperior foam as evidenced by the lower liquid volume collected in thegraduated cylinder.

Replacement of Ethoxylate Alcohol Surfactants. A reaction product wasformed by reacting maltodextrin with a mixture of dodecanoic acid (C₁₂fatty acid) and myristic acid (C₁₄ fatty acid) in the presence ofCocoDEA under the general conditions specified above. The reactionproduct was an opaque fluid, and no settling was observed. Similar tocertain data above, the reaction product did not afford significantemulsification of crude oil. The reaction product was formulated at astandard concentration (Sample BB), as well as at half the standardconcentration and double the standard concentration (Samples AA and CC,respectively). Surface tension, intrafacial tension, and contact anglevalues for these fluids are specified in Table 12 below.

Surface tension, intrafacial tension, and contact angle values for threeoilfield friction-reducing fluids containing ethoxylated alcoholsurfactants are also shown in Table 12 (Oilfield Fluids 1-3).

The ethoxylated alcohol surfactants in oilfield friction-reducing fluids1-3 were replaced with an equivalent quantity of reaction productobtained from double-concentration Sample CC. Surface tension,intrafacial tension, and contact angle values for the modified oilfieldfriction reducing fluids are specified in Table 12. The modifiedoilfield fluids are designated Oilfield Fluids 1′, 2′ and 3′,respectively.

TABLE 12 Concen- Surface Intrafacial Contact tration Tension TensionAngle Sample (gpt) (dynes/cm) (dynes/cm) (°) AA 1 28.1 1.4 20.3 2 28.00.6 n/d BB 1 32.7 3.4 27.2 2 29.8 1.8 n/d CC 1 40.2 7.0 39.8 2 32.8 3.8n/d Oilfield 1 31.66 2.02 31.3 Fluid 1 2 29.45 1.11 n/d Oilfield 1 33.963.17 33.7 Fluid 2 2 30.60 2.06 n/d Oilfield 1 30.45 1.85 30.8 Fluid 3 228.76 0.98 n/d Oilfield 1 28.25 0.36 29.6 Fluid 1′ 2 27.79 0.27 n/dOilfield 1 30.06 0.74 33.2 Fluid 2′ 2 28.14 0.56 n/d Oilfield 1 28.980.41 28.9 Fluid 3′ 2 27.79 0.30 n/dAs shown in Table 12, replacement of the ethoxylated alcohol surfactantin Oilfield Fluids 1-3 with a reaction product of the present disclosureafforded considerably lower surface tension and intrafacial tensionvalues in each case. Surprisingly, the surface tension and intrafacialtension values were even lower than in the Sample CC reaction productitself. Moreover, the friction-reducing properties of Oilfield Fluids1′-3′ were not significantly changed from original Oilfield Fluids 1-3(data not shown).

Unless otherwise indicated, all numbers expressing quantities and thelike in the present specification and associated claims are to beunderstood as being modified in all instances by the term “about.”Accordingly, unless indicated to the contrary, the numerical parametersset forth in the following specification and attached claims areapproximations that may vary depending upon the desired propertiessought to be obtained by the embodiments of the present invention. Atthe very least, and not as an attempt to limit the application of thedoctrine of equivalents to the scope of the claim, each numericalparameter should at least be construed in light of the number ofreported significant digits and by applying ordinary roundingtechniques.

One or more illustrative embodiments incorporating various features arepresented herein. Not all features of a physical implementation aredescribed or shown in this application for the sake of clarity. It isunderstood that in the development of a physical embodimentincorporating the embodiments of the present invention, numerousimplementation-specific decisions must be made to achieve thedeveloper's goals, such as compliance with system-related,business-related, government-related and other constraints, which varyby implementation and from time to time. While a developer's effortsmight be time-consuming, such efforts would be, nevertheless, a routineundertaking for those of ordinary skill in the art and having benefit ofthis disclosure.

While various systems, compositions, tools and methods are describedherein in terms of “comprising” various components or steps, thesystems, compositions, tools and methods can also “consist essentiallyof” or “consist of” the various components and steps.

As used herein, the phrase “at least one of” preceding a series ofitems, with the terms “and” or “or” to separate any of the items,modifies the list as a whole, rather than each member of the list (i.e.,each item). The phrase “at least one of” allows a meaning that includesat least one of any one of the items, and/or at least one of anycombination of the items, and/or at least one of each of the items. Byway of example, the phrases “at least one of A, B, and C” or “at leastone of A, B, or C” each refer to only A, only B, or only C; anycombination of A, B, and C; and/or at least one of each of A, B, and C.

Therefore, the disclosed systems, compositions, tools and methods arewell adapted to attain the ends and advantages mentioned as well asthose that are inherent therein. The particular embodiments disclosedabove are illustrative only, as the teachings of the present disclosuremay be modified and practiced in different but equivalent mannersapparent to those skilled in the art having the benefit of the teachingsherein. Furthermore, no limitations are intended to the details ofconstruction or design herein shown, other than as described in theclaims below. It is therefore evident that the particular illustrativeembodiments disclosed above may be altered, combined, or modified andall such variations are considered within the scope of the presentdisclosure. The systems, compositions, tools and methods illustrativelydisclosed herein may suitably be practiced in the absence of any elementthat is not specifically disclosed herein and/or any optional elementdisclosed herein. While systems, compositions, tools and methods aredescribed in terms of “comprising,” “containing,” or “including” variouscomponents or steps, the systems, tools and methods can also “consistessentially of” or “consist of” the various components and steps. Allnumbers and ranges disclosed above may vary by some amount. Whenever anumerical range with a lower limit and an upper limit is disclosed, anynumber and any included range falling within the range is specificallydisclosed. In particular, every range of values (of the form, “fromabout a to about b,” or, equivalently, “from approximately a to b,” or,equivalently, “from approximately a-b”) disclosed herein is to beunderstood to set forth every number and range encompassed within thebroader range of values. Also, the terms in the claims have their plain,ordinary meaning unless otherwise explicitly and clearly defined by thepatentee. Moreover, the indefinite articles “a” or “an,” as used in theclaims, are defined herein to mean one or more than one of the elementsthat it introduces. If there is any conflict in the usages of a word orterm in this specification and one or more patent or other documentsthat may be incorporated herein by reference, the definitions that areconsistent with this specification should be adopted.

What is claimed is the following:
 1. A composition comprising: anaqueous phase comprising an aqueous carrier fluid; a neutral surfactantor a reaction product thereof; and a reaction product of a saccharidepolymer and a fatty acid, the saccharide polymer comprising a dextran, adextrin compound, or any combination thereof, wherein the fatty acidconsists of one or more straight chain fatty acids comprising about 4 toabout 30 carbon atoms; wherein the neutral surfactant or the reactionproduct thereof and the reaction product of the saccharide polymer andthe fatty acid are dissolved as a solution in the aqueous phase; andwherein the reaction product of the saccharide polymer and the fattyacid is present at a concentration effective to lower a surface tensionof the neutral surfactant in the aqueous phase.
 2. The composition ofclaim 1, wherein the saccharide polymer comprises a dextrin compound andthe dextrin compound comprises a maltodextrin.
 3. The composition ofclaim 1, wherein the fatty acid comprises at least one fatty acidselected from the group consisting of butyric acid, valeric acid,caproic acid, enanthic acid, caprylic acid, pelabonic acid, capric acid,undecylic acid, lauric acid, tridecylic acid, myristic acid,pentadecylic acid, palmitic acid, margaric acid, stearic acid,nonadecylic acid, arachidic acid, heneicosylic acid, behenic acid,trioscylic acid, lignoceric acid, pentacosylic acid, cerotic acid,carboceric acid, montanic acid, nonacosylic acid, melissic acid,crotonic acid, cervonic acid, linoleic acid, linolelaidic acid,linolenic acid, arachidonic acid, docosatetraenoic acid, myristoleicacid, palmitoleic acid, sappenic acid, vaccenic acid, paullinic acid,oleic acid, pinolenic acid, stearidonic acid, eleostearic acid, elaidicacid, gondoic acid, gadoleic acid, erucic acid, eicosenoic acid,eicosadiencoic acid, eicosatrienoic acid, eicosatetraenoic acid,docosadienoic acid, nervonic acid, mead acid, adrenic acid, and anycombination thereof.
 4. The composition of claim 1, wherein the neutralsurfactant comprises cocamide diethanolamine or a reaction productthereof.
 5. The composition of claim 1, wherein the reaction product ofthe saccharide polymer and the fatty acid is formed in the presence ofthe neutral surfactant.
 6. The composition of claim 1, wherein a molarratio of fatty acid to saccharide polymer in the reaction product isabout 0.2 or above on a basis ofmoles_(fatty acid):moles_(glucose monomers).
 7. The composition of claim1, wherein the reaction product of the saccharide polymer is obtained inthe presence of water and a hydroxide base.
 8. The composition of claim1, wherein the reaction product of the saccharide polymer comprises afatty ester reaction product.
 9. A foamable formulation comprising thecomposition of claim
 1. 10. The foamable formulation of claim 9, whereinthe foamable formulation comprises a soap.
 11. A method comprising:providing an aqueous fluid comprising the composition of claim 1; andinducing foam formation in the aqueous fluid.
 12. The method of claim11, wherein inducing foam formation comprises agitating the aqueousfluid to introduce gas thereto as a plurality of bubbles.
 13. Thecomposition of claim 1, wherein a molar ratio of fatty acid tosaccharide polymer in the reaction product is about 0.2 to about 1.0 ona basis of moles_(fatty acid):moles_(glucose monomers).